Ethylene polymer product and film

Abstract

An ethylene polymer product with improved barrier properties is provided. The ethylene polymer product includes a bimodal polyethylene blend and a third ethylene polymer. The bimodal polyethylene blend comprises two narrow polydispersity ethylene polymers with mismatched molecular weights; namely: a first ethylene polymer and a second ethylene polymer. The third ethylene polymer possesses specifically defined calorimetric and molecular weight characteristics.

Description

[0001] ETHYLENE POLYMER PRODUCT AND FILM

[0002] TECHNICAL FIELD

[0003] The present disclosure relates to ethylene polymer products which when converted to film have good barrier properties.

[0004] BACKGROUND ART

[0005] Polyethylene materials are extensively utilized as packaging materials for food products. An important consideration in designing suitable food packaging is limiting the permeability of the structure to small molecule permeants, such as oxygen and moisture. One established method to enhance barrier properties is the incorporation of high-density polyethylenes (HDPEs) into the packaging structure. However, this method can lead to abrasive wear or “dusting” of the HDPE component when it comes into direct contact with film production and conversion machinery, thereby restricting the use of HDPEs in the outermost layer of the packaging structure. It is known that the addition of mineral antiblock additives can enhance the resistance of HDPE materials to abrasive wear; however, depending on their concentration, these additives can significantly compromise the barrier properties. Therefore, there remains a need for new polyethylene materials that exhibit low dusting propensity without compromising barrier properties.

[0006] SUMMARY OF INVENTION

[0007] Provided in a first aspect is an ethylene polymer product, comprising: A) a bimodal polyethylene blend; and B) from about 1×102parts per million to about 1×105parts per million of a third ethylene polymer, based on the total weight of the bimodal polyethylene blend. The bimodal polyethylene blend includes at least two identifiable blend components, namely: a first ethylene polymer having a first weight-average molecular weight, Mw,1, of from about 50 kg / mol to about 250 kg / mol, a first poly dispersity index, Mw,1 / Mn,1, of from about 1.7 to about 2.5, and a first density ρ1 of greater than about 0.94 g / cm3; and a second ethylene polymer having a second weight-average molecular weight, Mw,2, of from about 8 kg / mol to about 30 kg / mol, a second poly dispersity index, Mw,2 / Mn,2, of from about 1.7 to about 2.5, and a second density pi of greater than about 0.95 g / cm3. The third ethylene polymer has a melting point of greater than 80°C, as determined by differential scanning calorimetry; and a third weight-average molecular weight, v,3, satisfying the inequality Afw,3<- / / w,2.In some embodiments of the first aspect, the ethylene polymer product further comprises C) from about 1 x 102parts per million to about 3×103parts per million of a nucleating agent, based on the total weight of the bimodal polyethylene blend.

[0008] In some embodiments of the first aspect, the nucleating agent in C) comprises a calcium salt of 1,2-cyclohexanedicarboxylic acid.

[0009] In some embodiments of the first aspect, the ethylene polymer product further comprises D) from about 5×102parts per million to about 104parts per million of an inorganic anti-blocking additive, based on the total weight of the bimodal polyethylene blend.

[0010] In some embodiments of the first aspect, the inorganic anti-blocking additive in D) comprises talc.

[0011] In some embodiments of the first aspect, the bimodal polyethylene blend is further characterized by at least one of the following features: (I) a poly dispersity index, Mw / Mn, of from about 4 to about 18; (II) a z-average molecular weight to number-average molecular weight ratio, Mz / Mn, of from about 8 to about 40; (III) a z-average molecular weight to weight-average molecular weight ratio, Mz / Mw, of from about 2 to about 5; (IV) a number-average molecular weight, Mn, of from about 5 kg / mol to about 25 kg / mol; (V) a weight-average molecular weight, Mw, of from about 60 kg / mol to about 180 kg / mol; and (VI) a z-average molecular weight, Mz, of from about 180 kg / mol to about 350 kg / mol.

[0012] In some embodiments of the first aspect, the first weight-average molecular weight, v,i, and the second weight-average molecular weight, A / w,2, satisfy the inequality 2 < v,i / A7W,2 < 20.

[0013] In some embodiments of the first aspect, the bimodal polyethylene blend is an in-situ blend. As used herein, the term “in-situ” refers to a process in which the ethylene polymer product is formed while polymerization is occurring and is herein distinguished from a physical “ex-situ” process.

[0014] In some embodiments of the first aspect, the bimodal polyethylene blend is an in-situ blend produced in a continuous solution-phase polymerization process, the continuous solution-phase polymerization process comprising: forming a first ethylene polymer in a first solution-phase polymerization reactor in the presence of a first single site catalyst system; and forming a second ethylene polymer in a second solution-phase polymerization reactor in the presence of a second single site catalyst system. In some embodiments of the first aspect, the first single site catalyst system and the second single site catalyst system are independently chosen and each comprise an unbridged phosphinimine catalyst. In someembodiments of the first aspect, the first single site catalyst system and the second single site catalyst system both comprise the same unbridged phosphinimine catalyst. In some embodiments of the first aspect, the first solution-phase polymerization reactor and the second solution-phase polymerization reactor are configured in series with one another.

[0015] In some embodiments of the first aspect, the first ethylene polymer has a weight percent of from about 30 weight percent to about 70 weight percent, based on the total weight of the bimodal polyethylene blend; and the second ethylene polymer has a weight percent of from about 30 weight percent to about 70 weight percent, based on the total weight of the bimodal polyethylene blend.

[0016] In some embodiments of the first aspect, the first ethylene polymer has a weight percent of greater than 50 weight percent, based on the total weight of the bimodal polyethylene blend — the first ethylene polymer is the major blend component.

[0017] In some embodiments of the first aspect, the second ethylene polymer has a weight percent of greater than 50 weight percent, based on the total weight of the bimodal polyethylene blend — the second ethylene polymer is the major blend component.

[0018] In some embodiments of the first aspect, the first ethylene polymer, the second ethylene polymer and the third ethylene polymer are each an ethylene homopolymer. In these embodiments, the term “ethylene homopolymer” is meant to convey a conventional meaning — i.e., the first ethylene polymer, the second ethylene polymer and the third ethylene polymer each essentially consists of ethylene monomer units. Those of ordinary skill in the art recognize that very minor amounts — e.g., less than 0.5 mol% — of a-olefinic comonomer units may be present in the “ethylene homopolymer” as a result of contamination of the ethylene stream and / or the polymerization medium.

[0019] In some embodiments of the first aspect, the third ethylene polymer has a heat of fusion of greater than 200 J / g, as determined by differential scanning calorimetry.

[0020] In some embodiments of the first aspect, the third ethylene polymer has a melting point of greater than 110°C, as determined by differential scanning calorimetry.

[0021] In some embodiments of the first aspect, the third ethylene polymer has a heat of fusion of greater than 200 J / g, as determined by differential scanning calorimetry; and a melting point of greater than 110°C, as determined by differential scanning calorimetry.

[0022] In some embodiments of the first aspect, the third ethylene polymer contains greater than about 60 weight percent, based on the total weight of the third ethylene polymer, of material having a molecular weight of greater than 1,000 g / mol and less than 10,000 g / mol.In some embodiments of the first aspect, the third ethylene polymer contains greater than about 70 weight percent, based on the total weight of the third ethylene polymer, of material having a molecular weight of greater than 1,000 g / mol and less than 10,000 g / mol.

[0023] In some embodiments of the first aspect, the third ethylene polymer has a third poly dispersity index, Mw,3 / Mn,3, satisfying the inequalities: 1< M / MHJ < 1.5xA / w,i / Mn,i and l< v,3 / Mn,3 < 1.5xA / w,2 / Mn,2.

[0024] In some embodiments of the first aspect, the third ethylene polymer has a third poly dispersity index, Mw,3 / Mn,3, of from greater than 1 to less than about 3.

[0025] In some embodiments of the first aspect, the ethylene polymer product has an overall density of greater than about 0.950 g / cm3and an overall melt index I2 of from about 0.5 g / 10 minute to about 15 g / 10 minute.

[0026] Provided in a second aspect is a film layer comprising the ethylene polymer product of the first aspect.

[0027] Provided in a third aspect is a multilayer film structure comprising the film layer of the second aspect.

[0028] Provided in a fourth aspect is a film layer comprising an ethylene polymer product, the ethylene polymer product comprising: A) a bimodal polyethylene blend; and B) from about 1×102parts per million to about 1×105parts per million of a third ethylene polymer, based on the total weight of the bimodal polyethylene blend. The bimodal polyethylene blend comprises from about 30 weight percent to about 70 weight percent, based on the total weight of the bimodal polyethylene blend, of a first ethylene polymer having a first weight-average molecular weight, Mw,i, of from about 50 kg / mol to about 250 kg / mol, a first poly dispersity index, Mw,i / Mn,i, of from about 1.7 to about 2.5, and a first density ρ1 of greater than about 0.94 g / cm3; and from about 70 weight percent to about 30 weight percent, based on the total weight of the bimodal polyethylene blend, of a second ethylene polymer having a second weight-average molecular weight, v,2, of from about 8 kg / mol to about 30 kg / mol, a second poly dispersity index, v,2 / Mn,2, of from about 1.7 to about 2.5, and a second density pi of greater than about 0.95 g / cm3. The third ethylene polymer has a melting point of greater than 80°C, as determined by differential scanning calorimetry; and a third weight-average molecular weight, Mp, satisfying the inequality Mp < v,2.

[0029] In some embodiments of the fourth aspect, the third ethylene polymer has a heat of fusion of greater than 200 J / g and a melting point of greater than 110°C, as determined by differential scanning calorimetry.In some embodiments of the fourth aspect, the third ethylene polymer has a third poly dispersity index, Mw,3 / Mn,3, of from greater than 1 to less than about 3.

[0030] In some embodiments of the fourth aspect, the third ethylene polymer contains greater than about 70 weight percent, based on the total weight of the third ethylene polymer, of material having a molecular weight of greater than 1,000 g / mol and less than 10,000 g / mol.

[0031] In some embodiments of the fourth aspect, the bimodal polyethylene blend is further characterized by at least one of the following features: (I) a poly dispersity index, Mw / Mn, of from about 4 to about 18; (II) a z-average molecular weight to number-average molecular weight ratio, Mz / Mn, of from about 8 to about 40; (III) a z-average molecular weight to weight-average molecular weight ratio, Mz / Mw, of from about 2 to about 5; (IV) a number-average molecular weight, Mn, of from about 5 kg / mol to about 25 kg / mol; (V) a weight-average molecular weight, Mw, of from about 60 kg / mol to about 180 kg / mol; and (VI) a z-average molecular weight, Mz, of from about 180 kg / mol to about 350 kg / mol.

[0032] In some embodiments of the fourth aspect, the bimodal polyethylene blend is an in-situ blend. As used herein, the term “in-situ” refers to a process in which the ethylene polymer product is formed while polymerization is occurring and is herein distinguished from a physical “ex-situ” process.

[0033] In some embodiments of the fourth aspect, the first ethylene polymer, the second ethylene polymer and the third ethylene polymer are each an ethylene homopolymer. In these embodiments, the term “ethylene homopolymer” is meant to convey a conventional meaning — i.e., the first ethylene polymer, the second ethylene polymer and the third ethylene polymer each essentially consists of ethylene monomer units. Those of ordinary skill in the art recognize that very minor amounts — e.g., less than 0.5 mol% — of a-olefinic comonomer units may be present in the “ethylene homopolymer” as a result of contamination of the ethylene stream and / or the polymerization medium.

[0034] In some embodiments of the fourth aspect, the ethylene polymer product has an overall density of greater than about 0.950 g / cm3and an overall melt index I2 of from about 0.5 g / 10 minute to about 15 g / 10 minute.

[0035] In some embodiments of the fourth aspect, the film layer is a blown film layer. In some embodiments of the fourth aspect, the film layer is a blown film layer and has a normalized water vapor transmission rate, nWVTR, of 0.10 g / 100 in2 / day or less at a film thickness of about 1.5 mil, wherein the normalized water vapor transmission rate is determined by multiplying the experimentally measured WVTR at 38°C and a relativehumidity of 100% by the actual film thickness in mils and subsequently dividing the result by 1.5 mils.

[0036] In some embodiments of the fourth aspect, the film layer is a blown film layer and has a normalized water vapor transmission rate, nWVTR, of 0.10 g / 100 in2 / day or less at a film thickness of about 1.5 mil. In these embodiments, the ethylene polymer product comprises: C) from about 1 x 102parts per million to about 3×103parts per million of a nucleating agent, based on the total weight of the bimodal polyethylene blend; and D) from about 5×102parts per million to about 1×104parts per million of an inorganic anti-blocking additive, based on the total weight of the bimodal polyethylene blend.

[0037] In some embodiments of the fourth aspect, the nucleating agent in C) comprises a calcium salt of 1,2-cyclohexanedicarboxylic acid.

[0038] In some embodiments of the fourth aspect, the inorganic anti-blocking additive in D) comprises talc.

[0039] In some embodiments of the fourth aspect, the film layer is a blown film layer and has a normalized oxygen transmission rate, nOTR, of 30 cm3 / 100 in2 / day or less at a film thickness of about 1.5 mil, wherein the normalized oxygen transmission rate is determined by multiplying the experimentally measured OTR at 23 °C and at a relative humidity of 0% by the actual film thickness in mils and subsequently dividing the result by 1.5 mils.

[0040] In some embodiments of the fourth aspect, the film layer is a blown film layer and has a normalized oxygen transmission rate, nOTR, of 30 cm3 / 100 in2 / day or less at a film thickness of about 1.5 mil. In these embodiments, the ethylene polymer product comprises: C’) from about 1 x 102parts per million to about 3 x 103parts per million of a nucleating agent, based on the total weight of the bimodal polyethylene blend; and D’) from about 5×102parts per million to about 1×104parts per million of an inorganic anti-blocking additive, based on the total weight of the bimodal polyethylene blend.

[0041] In some embodiments of the fourth aspect, the nucleating agent in C’) comprises a calcium salt of 1,2-cyclohexanedicarboxylic acid.

[0042] In some embodiments of the fourth aspect, the inorganic anti-blocking additive in D’) comprises talc.

[0043] Provided in a fifth aspect is a multilayer film structure comprising the film layer of the fourth aspect.

[0044] In some embodiments of the fifth aspect, the film layer is a skin layer — i.e., the film layer of the fourth aspect is placed in a skin layer of the multilayer film structure of the fifth aspect.Provided in a sixth aspect is a multilayer film structure, comprising at least one skin layer comprising an ethylene polymer product. The ethylene polymer product comprises A) a bimodal polyethylene blend; B) from about 1×102parts per million to about 1×105parts per million of a third ethylene polymer, based on the total weight of the bimodal polyethylene blend; C) from about 1 x 102parts per million to about 3 x 103parts per million of a nucleating agent, based on the total weight of the bimodal polyethylene blend; and D) from about 5×102parts per million to about 1×104parts per million of an inorganic antiblocking additive, based on the total weight of the bimodal polyethylene blend. The bimodal polyethylene blend comprises from about 30 weight percent to about 70 weight percent, based on the total weight of the bimodal polyethylene blend, of a first ethylene polymer having a first weight-average molecular weight, Mw,1, of from about 50 kg / mol to about 250 kg / mol, a first poly dispersity index, Mw,1 / Mn,1, of from about 1.7 to about 2.5, and a first density ρ1 of greater than about 0.94 g / cm3; and from about 70 weight percent to about 30 weight percent, based on the total weight of the bimodal polyethylene blend, of a second ethylene polymer having a second weight-average molecular weight, Mw,2, of from about 8 kg / mol to about 30 kg / mol, a second poly dispersity index, Mw,2 / Mn,2, of from about 1.7 to about 2.5, and a second density pi of greater than about 0.95 g / cm3. The third ethylene polymer has a melting point of greater than 80°C, as determined by differential scanning calorimetry; and a third weight-average molecular weight, v,3, satisfying the inequality Afw,3<- / / w,2.

[0045] In some embodiments of the sixth aspect, the nucleating agent in C) comprises a calcium salt of 1,2-cyclohexanedicarboxylic acid.

[0046] In some embodiments of the sixth aspect, the inorganic anti-blocking additive in D) comprises talc.

[0047] In some embodiments of the sixth aspect, the third ethylene polymer has a heat of fusion of greater than 200 J / g and a melting point of greater than 110°C, as determined by differential scanning calorimetry.

[0048] In some embodiments of the sixth aspect, the third ethylene polymer has a third poly dispersity index, Mw,3 / Mn,3, of from greater than 1 to less than about 3.

[0049] In some embodiments of the sixth aspect, the third ethylene polymer contains greater than about 70 weight percent, based on the total weight of the third ethylene polymer, of material having a molecular weight of greater than 1,000 g / mol and less than 10,000 g / mol.

[0050] In some embodiments of the sixth aspect, the bimodal polyethylene blend is further characterized by at least one of the following features: (I) a poly dispersity index, Mw / Mn, offrom about 4 to about 18; (II) a z-average molecular weight to number-average molecular weight ratio, Mz / Mn, of from about 8 to about 40; (III) a z-average molecular weight to weight-average molecular weight ratio, Mz / Mw, of from about 2 to about 5; (IV) a number-average molecular weight, Mn, of from about 5 kg / mol to about 25 kg / mol; (V) a weight-average molecular weight, Mw, of from about 60 kg / mol to about 180 kg / mol; and (VI) a z-average molecular weight, Mz, of from about 180 kg / mol to about 350 kg / mol.

[0051] In some embodiments of the sixth aspect, the bimodal polyethylene blend is an in-situ blend. As used herein, the term “in-situ” refers to a process in which the ethylene polymer product is formed while polymerization is occurring and is herein distinguished from a physical “ex-situ” process.

[0052] In some embodiments of the sixth aspect, the first ethylene polymer, the second ethylene polymer and the third ethylene polymer are each an ethylene homopolymer. In these embodiments, the term “ethylene homopolymer” is meant to convey a conventional meaning — i.e., the first ethylene polymer, the second ethylene polymer and the third ethylene polymer each essentially consists of ethylene monomer units. Those of ordinary skill in the art recognize that very minor amounts — e.g., less than 0.5 mol% — of a-olefinic comonomer units may be present in the “ethylene homopolymer” as a result of contamination of the ethylene stream and / or the polymerization medium.

[0053] In some embodiments of the sixth aspect, the ethylene polymer product has an overall density of greater than about 0.950 g / cm3and an overall melt index I2 of from about 0.5 g / 10 minute to about 15 g / 10 minute.

[0054] Definitions

[0055] Other than in the examples or where otherwise indicated, all numbers or expressions referring to quantities of ingredients, extrusion conditions, etc., used in the specification and claims are to be understood as modified in all instances by the term “about”. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that can vary depending upon the desired properties that the various embodiments desire to obtain. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. The numerical values set forth in the specific examples are reported as precisely as possible. Any numerical values, however, inherently contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.It should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of “1 to 10” is intended to include all sub-ranges between and including the recited minimum value of 1 and the recited maximum value of 10; that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10. Because the disclosed numerical ranges are continuous, they include every value between the minimum and maximum values. Unless expressly indicated otherwise, the various numerical ranges specified in this application are approximations.

[0056] All compositional ranges expressed herein are limited in total to and do not exceed 100 percent (volume percent or weight percent) in practice. Where multiple components can be present in a composition, the sum of the maximum amounts of each component can exceed 100 percent, with the understanding that, and as those skilled in the art readily understand, that the amounts of the components actually used will conform to the maximum of 100 percent.

[0057] To form a more complete understanding of this disclosure the following terms are defined and should be used with the accompanying description of the various embodiments throughout.

[0058] As used herein, the term “monomer” refers to a small molecule that may chemically react and become chemically bonded with itself or other monomers to form a polymer.

[0059] As used herein, the term “a-olefin” or “alpha-olefin” is used to describe a monomer having a linear hydrocarbon chain having a double bond at one end of the chain and containing from n = 3 to 20 carbon atoms with a chemical formula CnH2n, an equivalent term is “linear a-olefin ”

[0060] As used herein, the terms “polyethylene”, “polyethylene polymer” or “ethylene polymer”, refers to macromolecules produced from ethylene monomer and optionally at least one a-olefin monomer; regardless of the specific catalyst or specific process used to make the ethylene polymer. An ethylene polymer in its polymerized form will include greater than 50 weight percent (based on the weight of the ethylene polymer) of ethylene monomeric units. Common polyethylenes include high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), ultralow density polyethylene (ULDPE), plastomer and elastomers. The term polyethylene also includes combinations of, or blends of, the polyethylenes described above.As used herein, the terms “sheet” and “film” refer to a web of material of any thickness.

[0061] As used herein the term “monolayer film” refers to a film containing a single layer of one or more than one thermoplastic polymer.

[0062] As used herein the term “multilayer film” or “multilayer film structure” refers to a film composed of more than one thermoplastic layer, or optionally non-thermoplastic layers. Non-limiting examples of non-thermoplastic materials include metals (foil) or cellulosic (paper) products. One or more of the thermoplastic layers within a multilayer film (or film structure) may be comprised of more than one thermoplastic.

[0063] As used herein, the terms “hydrocarbyl”, “hydrocarbyl radical” or “hydrocarbyl group” refers to linear or cyclic, aliphatic, olefinic, acetylenic and aryl (aromatic) radicals comprising hydrogen and carbon that are deficient by one hydrogen.

[0064] As used herein, an “alkyl radical” includes linear, branched and cyclic paraffin radicals that are deficient by one hydrogen radical; non-limiting examples include methyl ( — CH3) and ethyl ( — CH2CH3) radicals. The term “alkenyl radical” refers to linear, branched and cyclic hydrocarbons containing at least one carbon-carbon double bond that is deficient by one hydrogen radical.

[0065] As used herein, the term “aryl” group includes phenyl, naphthyl, pyridyl and other radicals whose molecules have an aromatic ring structure; non-limiting examples include naphthylene, phenanthrene and anthracene. An “arylalkyl” group is an alkyl group having an aryl group pendant there from; non-limiting examples include benzyl, phenethyl and tolylmethyl; an “alkylaryl” is an aryl group having one or more alkyl groups pendant there from; non-limiting examples include tolyl, xylyl, mesityl and cumyl.

[0066] As used herein, the phrase “heteroatom” includes any atom other than carbon and hydrogen that can be bound to carbon. A “heteroatom-containing group” is a hydrocarbon radical that contains a heteroatom and may contain one or more of the same or different heteroatoms. In one embodiment, a heteroatom-containing group is a hydrocarbyl group containing from 1 to 3 atoms selected from the group consisting of boron, aluminum, silicon, germanium, nitrogen, phosphorous, oxygen and sulfur. Non-limiting examples of heteroatom-containing groups include radicals of imines, amines, oxides, phosphines, ethers, ketones, oxoazolines heterocyclics, oxazolines, thioethers, and the like. The term “heterocyclic” refers to ring systems having a carbon backbone that comprise from 1 to 3 atoms selected from the group consisting of boron, aluminum, silicon, germanium, nitrogen, phosphorous, oxygen and sulfur.As used herein the term “unsubstituted” means that hydrogen radicals are bounded to the molecular group that follows the term unsubstituted. The term “substituted” means that the group following this term possesses one or more moieties that have replaced one or more hydrogen radicals in any position within the group; non-limiting examples of moieties include halogen radicals (F, Cl, Br), hydroxyl groups, carbonyl groups, carboxyl groups, amine groups, phosphine groups, alkoxy groups, phenyl groups, naphthyl groups, Ci to C30 alkyl groups, C2 to C30 alkenyl groups, and combinations thereof. Non-limiting examples of substituted alkyls and aryls include: acyl radicals, alkylamino radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- and dialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals, arylamino radicals and combinations thereof.

[0067] DESCRIPTION OF EMBODIMENTS

[0068] In the present disclosure, the ethylene polymer product will include a bimodal polyethylene blend and a third ethylene polymer. The bimodal polyethylene blend comprises two narrow poly dispersity ethylene polymers with mismatched molecular weights: a first ethylene polymer and a second ethylene polymer. The third ethylene polymer possesses specifically defined calorimetric and molecular weight characteristics. Each of these ethylene polymers, as well as the ethylene polymer product of which they are each a part are further described below.

[0069] Bimodal Polyethylene Blend

[0070] The bimodal polyethylene blend is a blend comprising a higher molecular weight component (first ethylene polymer) and a lower molecular weight component (the second ethylene polymer). The bimodal polyethylene blend will have a bimodal molecular weight distribution generated by the conventional gel permeation chromatography technique disclosed in the Testing Methods section. The term “bimodal” connotes the presence of two discernable maxima in a molecular weight distribution curve generated by the conventional gel permeation chromatography technique disclosed in the Testing Methods section.

[0071] Alternatively, by the term “bimodal”, it is meant that in addition to a first peak in a gel permeation chromatograph generated by the conventional gel permeation chromatography technique disclosed in the Testing Methods section, there will be a secondary peak, shoulder or tail which represents a higher or lower molecular weight component — i.e., the molecular weight distribution can be said to have two discernable maxima in a molecular weight distribution curve using mathematical deconvolution and / or through reaction simulation.In embodiments of the disclosure, the bimodal polyethylene blend consists essentially of the first ethylene polymer and the second ethylene polymer.

[0072] In embodiments of the disclosure, the bimodal polyethylene blend has a

[0073] polydispersity index, Mᵂ / Mₙ, of from about 4 to about 18, or from about 4.5 to about 17, or from about 5 to about 15, or from about 7 to about 15, or from about 7 to about 14, or from about 7 to about 12.

[0074] In embodiments of the disclosure, the bimodal polyethylene blend has a z-average molecular weight to number-average molecular weight ratio, Mz / Mn, of from about 8 to about 40, or from about 10 to about 40, or from about 12 to about 40, from about 15 to about 40, or from about 18 to about 38.

[0075] In embodiments of the disclosure, the bimodal polyethylene blend has a z-average molecular weight to weight-average molecular weight ratio, Mz / Mw, of from about 2 to about 5, or from about 2.1 to about 5, or from about 2.3 to about 5, or from about 2.5 to about 5, or from about 2.6 to about 5, or from about 2.65 to about 5, or from about 2.3 to about 4.5, or from about 2.3 to about 4, or from about 2.5 to about 4.

[0076] In embodiments of the disclosure, the bimodal polyethylene blend has a number-average molecular weight, Mn, of from about 5 kg / mol to about 25 kg / mol, or from about 5 kg / mol to about 20 kg / mol, or from about 5 kg / mol to about 18 kg / mol, or from about 5 kg / mol to about 15 kg / mol, or from about 6 kg / mol to about 15 kg / mol, or from about 8 kg / mol to about 15 kg / mol, or from about 8 kg / mol to about 12 kg / mol.

[0077] In embodiments of the disclosure, the bimodal polyethylene blend has a weight-average molecular weight, Mw, of from about 60 kg / mol to about 180 kg / mol, or from about 65 kg / mol to about 160 kg / mol, or from about 65 kg / mol to about 150 kg / mol, or from about 65 kg / mol to about 140 kg / mol, or from about 70 kg / mol to about 140 kg / mol.

[0078] In embodiments of the disclosure, the bimodal polyethylene blend has a z-average molecular weight, Mz, of from about 180 kg / mol to about 350 kg / mol, or from about 190 kg / mol to about 340 kg / mol, or from about 190 kg / mol to about 320 kg / mol, or from about 190 kg / mol to about 300 kg / mol.

[0079] First Ethylene Polymer

[0080] The first ethylene polymer is the higher molecular weight component in the bimodal polyethylene blend. The term “higher molecular weight component” is defined in relation to the “lower molecular weight component”, meaning the higher molecular weight component has a weight-average molecular weight, MWHMWgreater than (>) that of the lower molecular weight component, MWLMW.The first ethylene polymer has a first weight-average molecular weight, Mw,1, of from about 50 kg / mol to about 250 kg / mol. In embodiments of the disclosure, the first ethylene polymer has a first weight-average molecular weight, Mw,1, of from about 70 kg / mol to about 250 kg / mol, or from about 75 kg / mol to about 250 kg / mol, or from about 80 kg / mol to about 250 kg / mol, or from about 85 kg / mol to about 250 kg / mol, or from about 90 kg / mol to about 250 kg / mol, or from about 85 kg / mol to about 250 kg / mol, or from about 90 kg / mol to about 250 kg / mol, or from about 100 kg / mol to about 250 kg / mol, or from about 105 kg / mol to about 250 kg / mol, or from about 110 kg / mol to about 250 kg / mol, or from about 120 kg / mol to about 250 kg / mol, or from about 125 kg / mol to about 250 kg / mol, or from about 125 kg / mol to about 225 kg / mol, or from about 125 kg / mol to about 215 kg / mol, or from about 125 kg / mol to about 210 kg / mol, or from about 125 kg / mol to about 205 kg / mol, or from about 125 kg / mol to about 200 kg / mol, or from about 130 kg / mol to about 200 kg / mol, or from about 130 kg / mol to about 195 kg / mol, or from about 130 kg / mol to about 190 kg / mol.

[0081] The first ethylene polymer is a narrow poly dispersity polymer and has a first polydispersity index, Mw,1 / Mn,1, of from about 1.7 to about 2.5. In embodiments of the disclosure, the first ethylene polymer has a Mw,1 / Mn,1 of from about 1.7 to about 2.3, or from about 1.7 to about 2.1, from about 1.7 to about 2.0. In embodiments of the disclosure, the first ethylene polymer has a Mw,1 / Mn,1 of about 2.0.

[0082] The first ethylene polymer has a first density ρ1 of greater than about 0.94 g / cm3. In embodiments of the disclosure, the first ethylene polymer has a first density ρ1 of greater than about 0.94 g / cm3and less than 0.97 g / cm3. In embodiments of the disclosure, the first ethylene polymer has a first density pi of greater than about 0.94 g / cm3and less than 0.965 g / cm3. In embodiments of the disclosure, the first ethylene polymer has a first density pi of greater than about 0.94 g / cm3and less than 0.96 g / cm3. In embodiments of the disclosure, the first ethylene polymer has a first density pi of greater than about 0.94 g / cm3and less than 0.955 g / cm3.

[0083] In embodiments of the disclosure, the first ethylene polymer is an ethylene homopolymer. The term “ethylene homopolymer” is meant to convey a conventional meaning — i.e., the first ethylene polymer essentially consists of ethylene monomer units. Those of ordinary skill in the art recognize that very minor amounts — e.g., less than 0.5 mol% — of a-olefinic comonomer units may be present in the “ethylene homopolymer” as a result of contamination of the ethylene stream and / or the polymerization medium.In embodiments of the disclosure, the first ethylene polymer has a weight percent of greater than 50 weight percent, based on the total weight of the bimodal polyethylene blend — i.e., the first ethylene polymer is the major component in the bimodal polyethylene blend.

[0084] In embodiments of the disclosure, the upper limit on the weight percent of the first ethylene polymer in the bimodal polyethylene blend (i.e., the weight percent of the first ethylene polymer based on the total weight of the bimodal polyethylene blend) is about 70 weight percent, or about 65 weight percent, or about 60 weight percent, or about 55 weight percent. In embodiments of the disclosure, the lower limit on the weight percent of the first ethylene polymer in the bimodal polyethylene blend (i.e., the weight percent of the first ethylene polymer based on the total weight of the bimodal polyethylene blend) is about 30 weight percent, or about 35 weight percent, or about 40 weight percent, or about 45 weight percent. In embodiments of the disclosure, the first ethylene polymer has a weight percent of from about 30 weight percent to about 70 weight percent, based on the total weight of the bimodal polyethylene blend. In embodiments of the disclosure, the first ethylene polymer has a weight percent of from about 40 weight percent to about 60 weight percent, based on the total weight of the bimodal polyethylene blend.

[0085] In embodiments of the disclosure, the first ethylene polymer is formed in the presence of a first single site catalyst system.

[0086] In some embodiments, the first ethylene polymer is formed in the presence of a first single site catalyst system that produces no or undetectable levels of long chain branching. Long chain branching, hereinafter “LCB”, is a well-known structural phenomenon in ethylene polymers to those of ordinary skill in the art. In the present disclosure, a long chain branch has a molecular weight equal to, or greater than, the entanglement molecular weight, Me. Me is a well-known concept in polymer physics (e.g., reported to be about 1 kg / mol for polyethylenes, see Fetters et al., Macromolecules 1999, 32, 6847). Presence of long chain branches in a sample can be detectable by comparing rheological test results with a comparative sample known to contain no long chain branches. Non-limiting examples of rheological test results include, flow activation energy (Ea), shear thinning or viscosity ratios, melt flow ratios (I21 / I2, 110 / I2, etc.), melt strength, etc.

[0087] In some embodiments, the first single site catalyst system comprises an unbridged phosphinimine catalyst.

[0088] In an embodiment, the unbridged phosphinimine catalyst is represented by formula:

[0089] (LA)aM(PI)b(Q)nwherein (LA) represents is cyclopentadienyl-type ligand; M represents a metal atom selected from the group consisting of Ti, Zr, and Hf; PI represents a phosphinimine ligand; Q represents an activatable ligand; a is 0 or 1; b is 1 or 2; (a+b) = 2; n is 1 or 2, and; the sum of (a+b+n) equals the valance of the metal M.

[0090] As used herein, the term “cyclopentadienyl-type” ligand is meant to include ligands which contain at least one five-carbon ring which is bonded to the metal via eta-5 (or in some cases eta-3) bonding. Thus, the term “cyclopentadienyl-type” includes, for example, unsubstituted cyclopentadienyl, singly or multiply substituted cyclopentadienyl, unsubstituted indenyl, singly or multiply substituted indenyl, unsubstituted fluorenyl and singly or multiply substituted fluorenyl. Hydrogenated versions of indenyl and fluorenyl ligands are also contemplated for use in the current disclosure, so long as the five-carbon ring which bonds to the metal via eta-5 (or in some cases eta-3) bonding remains intact. Substituents for a cyclopentadienyl ligand, an indenyl ligand (or hydrogenated version thereof) and a fluorenyl ligand (or hydrogenated version thereof) may be selected from the group consisting of a C1-30 hydrocarbyl radical (which hydrocarbyl radical may be unsubstituted or further substituted by for example a halide and / or a hydrocarbyl group; for example a suitable substituted C1-30 hydrocarbyl radical is a pentafluorobenzyl group such as -CH2C6F5); a halogen atom; a C1-8 alkoxy radical; a C6-10 aryl or aryloxy radical (each of which may be further substituted by for example a halide and / or a hydrocarbyl group); an amido radical which is unsubstituted or substituted by up to two C1-8 alkyl radicals; a phosphido radical which is unsubstituted or substituted by up to two C1-8 alkyl radicals; a silyl radical of the formula -Si(R')3 wherein each R' is independently selected from the group consisting of hydrogen, a C1-8 alkyl or alkoxy radical, C6-10 aryl or aryloxy radicals; and a germanyl radical of the formula -Ge(R')3 wherein R' is as defined directly above.

[0091] The phosphinimine ligand, PI, is defined by formula:

[0092] (RP)3P = N -wherein the Rpgroups are independently selected from: a hydrogen atom; a halogen atom; C1-20 hydrocarbyl radicals which are unsubstituted or substituted with one or more halogen atom(s); a C1-8 alkoxy radical; a C6-10 aryl radical; a C6-10 aryloxy radical; an amido radical; a silyl radical of formula -Si(Rs)3, wherein the Rs groups are independently selected from, a hydrogen atom, a C1-8 alkyl or alkoxy radical, a C6-10 aryl radical, a C6-10 aryloxy radical, or a germanyl radical of formula -Ge(RG)3, wherein the RGgroups are defined as Rsis defined in this paragraph.In an embodiment of the disclosure, the metal, M in the unbridged phosphinimine catalyst is titanium, Ti.

[0093] In an embodiment of the disclosure, the first single site catalyst system comprises cyclopentadienyl tri(tertiarybutyl)phosphinimine titanium dichloride, Cp((t-Bu)3PN)TiCh.

[0094] Second Ethylene Polymer

[0095] The second ethylene polymer is the lower molecular weight component in the bimodal polyethylene blend. The term “lower molecular weight component” is defined in relation to the “higher molecular weight component”, meaning the lower molecular weight component has a weight-average molecular weight, MWLMWless than (<) that of the higher molecular weight component, MWHMW

[0096] The second ethylene polymer has a second weight-average molecular weight, Mw,2, of from about 8 kg / mol to about 30 kg / mol. In embodiments of the disclosure, the second ethylene polymer has a second weight-average molecular weight, Mw,2, of from about 8 kg / mol to about 25 kg / mol, or from about 9 kg / mol to about 25 kg / mol, or from about 10 kg / mol to about 25 kg / mol, or from about 10 kg / mol to about 20 kg / mol, or from about 8 kg / mol to about 20 kg / mol, or from about 8 kg / mol to about 18 kg / mol, or from about 8 kg / mol to about 16 kg / mol, or from about 8 kg / mol to about 15 kg / mol.

[0097] The second ethylene polymer is a narrow poly dispersity polymer and has a second polydispersity index, Mw,2 / Mn,2, of from about 1.7 to about 2.5. In embodiments of the disclosure, the second ethylene polymer has a Mw,2 / Mn,2 of from about 1.7 to about 2.3, or from about 1.7 to about 2.1, from about 1.7 to about 2.0. In embodiments of the disclosure, the second ethylene polymer has a Mw,2 / Mn,2 of about 2.0.

[0098] The second ethylene polymer has a second density pi of greater than about 0.95 g / cm3. In embodiments of the disclosure, the second ethylene polymer has a second density pi of greater than about 0.95 g / cm3and less than 0.985 g / cm3. In embodiments of the disclosure, the second ethylene polymer has a second density pi of greater than about 0.95 g / cm3and less than 0.98 g / cm3. In embodiments of the disclosure, the second ethylene polymer has a second density pi of greater than about 0.95 g / cm3and less than 0.975 g / cm3. In embodiments of the disclosure, the second ethylene polymer has a second density pi of greater than about 0.955 g / cm3and less than 0.975 g / cm3. In embodiments of the disclosure, the second ethylene polymer has a second density pi of greater than about 0.96 g / cm3and less than 0.975 g / cm3.

[0099] In some embodiments, the second ethylene polymer has a second density pi greater than the density of the first ethylene polymer, pi.In embodiments of the disclosure, the second ethylene polymer is an ethylene homopolymer. The term “ethylene homopolymer” is meant to convey a conventional meaning — i.e., the second ethylene polymer essentially consists of ethylene monomer units. Those of ordinary skill in the art recognize that very minor amounts — e.g., less than 0.5 mol% — of a-olefinic comonomer units may be present in the “ethylene homopolymer” as a result of contamination of the ethylene stream and / or the polymerization medium.

[0100] In embodiments of the disclosure, the second ethylene polymer has a weight percent of greater than 50 weight percent, based on the total weight of the bimodal polyethylene blend — i.e., the second ethylene polymer is the major component in the bimodal polyethylene blend.

[0101] In embodiments of the disclosure, the upper limit on the weight percent of the second ethylene polymer in the bimodal polyethylene blend (i.e., the weight percent of the second ethylene polymer based on the total weight of the bimodal polyethylene blend) is about 70 weight percent, or about 65 weight percent, or about 60 weight percent, or about 55 weight percent. In embodiments of the disclosure, the lower limit on the weight percent of the second ethylene polymer in the bimodal polyethylene blend (i.e., the weight percent of the second ethylene polymer based on the total weight of the bimodal polyethylene blend) is about 30 weight percent, or about 35 weight percent, or about 40 weight percent, or about 45 weight percent. In embodiments of the disclosure, the second ethylene polymer has a weight percent of from about 30 weight percent to about 70 weight percent, based on the total weight of the bimodal polyethylene blend. In embodiments of the disclosure, the second ethylene polymer has a weight percent of from about 40 weight percent to about 60 weight percent, based on the total weight of the bimodal polyethylene blend.

[0102] In embodiments of the disclosure, the second ethylene polymer is formed in the presence of a second single site catalyst system.

[0103] In some embodiments, the second ethylene polymer is formed in the presence of a second single site catalyst system that produces no or undetectable levels of long chain branching. Long chain branching, hereinafter “LCB”, is a well-known structural phenomenon in ethylene polymers to those of ordinary skill in the art. In the present disclosure, a long chain branch has a molecular weight equal to, or greater than, the entanglement molecular weight, Me. Meis a well-known concept in polymer physics (e.g., reported to be about 1 kg / mol for polyethylenes, see Fetters et al., Macromolecules 1999, 32, 6847). Presence of long chain branches in a sample can be detectable by comparing rheological test results with a comparative sample known to contain no long chain branches.Non-limiting examples of rheological test results include, flow activation energy (Ea), shear thinning or viscosity ratios, melt flow ratios (I21 / I2, I10 / I2, etc.), melt strength, etc.

[0104] In some embodiments, the second single site catalyst system comprises an unbridged phosphinimine catalyst.

[0105] In an embodiment, the unbridged phosphinimine catalyst is represented by formula:

[0106] (LA)aM(PI)b(Q)n

[0107] wherein (LA) represents is cyclopentadienyl-type ligand; M represents a metal atom selected from the group consisting of Ti, Zr, and Hf; PI represents a phosphinimine ligand; Q represents an activatable ligand; a is 0 or 1; b is 1 or 2; (a+b) = 2; n is 1 or 2, and; the sum of (a+b+n) equals the valance of the metal M.

[0108] As used herein, the term “cyclopentadienyl-type” ligand is meant to include ligands which contain at least one five-carbon ring which is bonded to the metal via eta-5 (or in some cases eta-3) bonding. Thus, the term “cyclopentadienyl-type” includes, for example, unsubstituted cyclopentadienyl, singly or multiply substituted cyclopentadienyl, unsubstituted indenyl, singly or multiply substituted indenyl, unsubstituted fluorenyl and singly or multiply substituted fluorenyl. Hydrogenated versions of indenyl and fluorenyl ligands are also contemplated for use in the current disclosure, so long as the five-carbon ring which bonds to the metal via eta-5 (or in some cases eta-3) bonding remains intact. Substituents for a cyclopentadienyl ligand, an indenyl ligand (or hydrogenated version thereof) and a fluorenyl ligand (or hydrogenated version thereof) may be selected from the group consisting of a C1-30 hydrocarbyl radical (which hydrocarbyl radical may be unsubstituted or further substituted by for example a halide and / or a hydrocarbyl group; for example a suitable substituted C1-30 hydrocarbyl radical is a pentafluorobenzyl group such as -CH2C6F5); a halogen atom; a C1-8 alkoxy radical; a C6-10 aryl or aryloxy radical (each of which may be further substituted by for example a halide and / or a hydrocarbyl group); an amido radical which is unsubstituted or substituted by up to two C1-8 alkyl radicals; a phosphido radical which is unsubstituted or substituted by up to two C1-8 alkyl radicals; a silyl radical of the formula -Si(R')3 wherein each R' is independently selected from the group consisting of hydrogen, a C1-8 alkyl or alkoxy radical, C6-10 aryl or aryloxy radicals; and a germanyl radical of the formula -Ge(R')3 wherein R' is as defined directly above.

[0109] The phosphinimine ligand, PI, is defined by formula:

[0110] (RP)3P = N -wherein the Rpgroups are independently selected from: a hydrogen atom; a halogen atom; Ci-20 hydrocarbyl radicals which are unsubstituted or substituted with one or more halogen atom(s); a C1-8 alkoxy radical; a C6-10 aryl radical; a C6-10 aryloxy radical; an amido radical; a silyl radical of formula -Si(Rs)3, wherein the Rs groups are independently selected from, a hydrogen atom, a C1-8 alkyl or alkoxy radical, a C6-10 aryl radical, a C6-10 aryloxy radical, or a germanyl radical of formula -Ge(RG)3, wherein the RGgroups are defined as Rsis defined in this paragraph.

[0111] In an embodiment of the disclosure, the metal, M in the unbridged phosphinimine catalyst is titanium, Ti.

[0112] In an embodiment of the disclosure, the second single site catalyst system comprises cyclopentadienyl tri(tertiarybutyl)phosphinimine titanium dichloride, Cp((t-Bu)3PN)TiCh.

[0113] Third Ethylene Polymer

[0114] The third ethylene polymer is present in the ethylene polymer product at a concentration ranging from about 1×102parts per million to about 1×105parts per million of a third ethylene polymer, based on the total weight of the bimodal polyethylene blend. In some embodiments, the third ethylene polymer is present in the ethylene polymer product at a concentration ranging from about 5×102parts per million to about 1 x 105parts per million of a third ethylene polymer, based on the total weight of the bimodal polyethylene blend. In some embodiments, the third ethylene polymer is present in the ethylene polymer product at a concentration ranging from about 0.1 x 104parts per million to about 1 x 105parts per million of a third ethylene polymer, based on the total weight of the bimodal polyethylene blend. In some embodiments, the third ethylene polymer is present in the ethylene polymer product at a concentration ranging from about 0.2x 104parts per million to about 1 x 105parts per million of a third ethylene polymer, based on the total weight of the bimodal polyethylene blend. In some embodiments, the third ethylene polymer is present in the ethylene polymer product at a concentration ranging from about 0.3 x 104parts per million to about 1 x 105parts per million of a third ethylene polymer, based on the total weight of the bimodal polyethylene blend. In some embodiments, the third ethylene polymer is present in the ethylene polymer product at a concentration ranging from about 0.5 x 104parts per million to about 1 x 105parts per million of a third ethylene polymer, based on the total weight of the bimodal polyethylene blend. In some embodiments, the third ethylene polymer is present in the ethylene polymer product at a concentration ranging from about 0.1×104parts per million to about 7×104parts per million of a third ethylene polymer, based on the total weight of the bimodal polyethylene blend. In some embodiments, the thirdethylene polymer is present in the ethylene polymer product at a concentration ranging from about 0.1×104parts per million to about 5×104parts per million of a third ethylene polymer, based on the total weight of the bimodal polyethylene blend. In some embodiments, the third ethylene polymer is present in the ethylene polymer product at a concentration ranging from about 0.1×104parts per million to about 3.5×104parts per million of a third ethylene polymer, based on the total weight of the bimodal polyethylene blend. In some embodiments, the third ethylene polymer is present in the ethylene polymer product at a concentration ranging from about 0.2×104parts per million to about 5×104parts per million of a third ethylene polymer, based on the total weight of the bimodal polyethylene blend. In some embodiments, the third ethylene polymer is present in the ethylene polymer product at a concentration ranging from about 0.3×104parts per million to about 5×104parts per million of a third ethylene polymer, based on the total weight of the bimodal polyethylene blend. In some embodiments, the third ethylene polymer is present in the ethylene polymer product at a concentration ranging from about 0.5×104parts per million to about 5×104parts per million of a third ethylene polymer, based on the total weight of the bimodal polyethylene blend. In some embodiments, the third ethylene polymer is present in the ethylene polymer product at a concentration ranging from about 0.5×104parts per million to about 3.5×104parts per million of a third ethylene polymer, based on the total weight of the bimodal polyethylene blend. In some embodiments, the third ethylene polymer is present in the ethylene polymer product at a concentration ranging from about 0.5×104parts per million to about 3×104parts per million of a third ethylene polymer, based on the total weight of the bimodal polyethylene blend.

[0115] The third ethylene polymer possesses specifically defined calorimetric properties, including a melting point of greater than 80°C, as determined by differential scanning calorimetry method described in the Testing Methods section. In some embodiments, the third ethylene polymer has a melting point of greater than 90°C, as determined by differential scanning calorimetry method described in the Testing Methods section. In some embodiments, the third ethylene polymer has a melting point of greater than 100°C, as determined by differential scanning calorimetry method described in the Testing Methods section. In some embodiments, the third ethylene polymer has a melting point of greater than 110°C, as determined by differential scanning calorimetry method described in the Testing Methods section. In some embodiments, the third ethylene polymer has a melting point of greater than 115°C, as determined by differential scanning calorimetry method described in the Testing Methods section.In some embodiments, the third ethylene polymer has a heat of fusion of greater than 175 J / g, as determined by differential scanning calorimetry method described in the Testing Methods section. In some embodiments, the third ethylene polymer has a heat of fusion of greater than 180 J / g, as determined by differential scanning calorimetry method described in the Testing Methods section. In some embodiments, the third ethylene polymer has a heat of fusion of greater than 190 J / g, as determined by differential scanning calorimetry method described in the Testing Methods section. In some embodiments, the third ethylene polymer has a heat of fusion of greater than 200 J / g, as determined by differential scanning calorimetry method described in the Testing Methods section. In some embodiments, the third ethylene polymer has a heat of fusion of greater than 210 J / g, as determined by differential scanning calorimetry method described in the Testing Methods section.

[0116] The third ethylene polymer will have a third weight-average molecular weight, v,3, satisfying the inequality v, 3 < v,2.

[0117] In some embodiment, the third ethylene polymer has a third weight-average molecular weight, Mw,3, of from about 1 kg / mol to about 14 kg / mol. In some embodiment, the third ethylene polymer has a third weight-average molecular weight, Mw,3, of from about 1 kg / mol to about 10 kg / mol. In some embodiment, the third ethylene polymer has a third weight-average molecular weight, Mw,3, of from about 1 kg / mol to about 8 kg / mol.

[0118] In some embodiments, the third ethylene polymer has a number-average molecular weight, Mn, of from about 0.5 kg / mol to about 10 kg / mol. In some embodiments, the third ethylene polymer has a number-average molecular weight, Mn, of from about 0.8 kg / mol to about 5 kg / mol. In some embodiments, the third ethylene polymer has a number-average molecular weight, Mn, of from about 0.8 kg / mol to about 4 kg / mol.

[0119] In some embodiments of the disclosure, the third ethylene polymer contains greater than about 60 weight percent, based on the total weight of the third ethylene polymer, of material having a molecular weight of greater than 1,000 g / mol and less than 10,000 g / mol. In some embodiments of the disclosure, the third ethylene polymer contains greater than about 65 weight percent, based on the total weight of the third ethylene polymer, of material having a molecular weight of greater than 1,000 g / mol and less than 10,000 g / mol. In some embodiments of the disclosure, the third ethylene polymer contains greater than about 70 weight percent, based on the total weight of the third ethylene polymer, of material having a molecular weight of greater than 1,000 g / mol and less than 10,000 g / mol. In some embodiments of the disclosure, the third ethylene polymer contains greater than about75 weight percent, based on the total weight of the third ethylene polymer, of material having a molecular weight of greater than 1,000 g / mol and less than 10,000 g / mol.

[0120] In some embodiments of the disclosure, the third ethylene polymer has a third poly dispersity index, Mw,3 / Mn,3, satisfying the inequalities: 1< M / MHJ < 1.5xA / w,i / Mn,i and l< v,3 / Mn,3 < 1.5>< v,2 / Mn,2. In some embodiments of the disclosure, the third ethylene polymer has a third poly dispersity index, v,3 / Mn,3, satisfying the inequalities: 1 < A7u.3 / Mn,3 < 1.3 xA / Wjl / Mn,l and 1 < A / w,3 / Mn,3 < 1.3 X fw,2 / Mn,2.

[0121] In some embodiments of the disclosure, the third ethylene polymer has a third polydispersity index, Mw,3 / Mn,3, of from greater than 1 to less than about 5, or from greater than 1 to less than about 4, or from greater than 1 to less than about 3, or from greater than 1 to less than about 2.5, or from greater than 1 to less than about 2.3, or from greater than 1 to less than about 2.1. In some embodiments of the disclosure, the third ethylene polymer has a third polydispersity index, Mw,3 / Mn,3, of from greater than 1 to less than about 2.0, or from greater than 1 to less than about 1.9, or from greater than 1 to less than about 1.8, or from greater than 1 to less than about 1.8, or from greater than 1 to less than about 1.7, or from greater than 1 to less than about 1.5.

[0122] In embodiments of the disclosure, the third ethylene polymer is an ethylene homopolymer. The term “ethylene homopolymer” is meant to convey a conventional meaning — i.e., the third ethylene polymer essentially consists of ethylene monomer units. Those of ordinary skill in the art recognize that very minor amounts — e.g., less than 0.5 mol% — of a-olefinic comonomer units may be present in the “ethylene homopolymer” as a result of contamination of the ethylene stream and / or the polymerization media.

[0123] In embodiments of the disclosure, the third ethylene polymer is produced in a high-pressure, free-radical polymerization process.

[0124] In embodiments of the disclosure, the third ethylene polymer is produced in a medium-pressure polymerization process in the presence of a suitable coordination catalyst.

[0125] In embodiments of the disclosure, the third ethylene polymer is produced in a low-pressure polymerization process in the presence of a suitable coordination catalyst.

[0126] In embodiments of the disclosure, the third ethylene polymer is formed in the presence of a single site catalyst.

[0127] In embodiments of the disclosure, the third ethylene polymer is formed in the presence of a Ziegler-Natta catalyst.In embodiments of the disclosure, the third ethylene polymer is produced by depolymerization of a high-molecular-weight ethylene polymer — i.e., a starting ethylene polymer having a Mw» Mw,3.

[0128] In embodiments of the disclosure, the third ethylene polymer is a synthetic polyethylene wax. Non-limiting examples of synthetic polyethylene waxes include LICOCENE® PE 4201 and LICOCENE® PE 5301, commercially available from Clariant International Ltd. Other non-limiting examples include POLYWAX® 3000, POLYWAX® 2000, POLYWAX® 1000, POLYWAX® 850 and POLYWAX® 400, commercially available from NuCera Solutions.

[0129] Ethylene Polymer Product

[0130] The ethylene polymer product disclosed herein can be made using any well-known technique in the art, including but not limited to melt blending, solution blending, or inreactor blending, or combinations thereof to bring together a first ethylene polymer, a second ethylene polymer and a third ethylene polymer. While the ethylene polymer product of the present disclosure will include a discernable bimodal polyethylene blend, the process used to make the ethylene polymer product is not limited to first forming a bimodal polyethylene blend as an intermediate precursor and then combining it with a third ethylene polymer to produce the ethylene polymer product.

[0131] It is contemplated by the present disclosure, that the ethylene polymer product of the present disclosure is made ex-situ by melt blending or solution blending: i) a first ethylene polymer; ii) a second ethylene polymer; and iii) a third ethylene polymer. As used herein, the term “ex-situ” refers to a process in which the ethylene polymer product is formed by combining the basic polymeric components wherein each one of the components is already polymerized and recovered from the polymerization process — the recovery operations can include catalyst deactivation, phase separation, devolatilizing unreacted monomers and / or process solvent, pelletization, etc. — before being combined with the other polymeric component(s).

[0132] It is also contemplated by the present disclosure, that the ethylene polymer product comprising a first, a second and a third ethylene polymer could be made in-situ in one or more polymerization reactor, using three different polymerization catalyst systems, where each polymerization catalyst system has a different response to one or more of hydrogen concentration, ethylene concentration, a-olefinic comonomer concentration (if present), and temperature under a given set of polymerization conditions, so that the first ethylene polymer is formed in the presence of a first polymerization catalyst system, the secondethylene polymer is formed in the presence of a second polymerization catalyst system and the third ethylene polymer is formed in the presence of a third polymerization catalyst system. As used herein, the term “in-situ” refers to a process in which the ethylene polymer product is formed while polymerization is occurring and is herein distinguished from a physical “ex-situ” process.

[0133] In an embodiment, the ethylene polymer product of the present disclosure is made in-situ by forming a first ethylene polymer in a first reactor by polymerizing ethylene in the presence of a first single site catalyst system; forming a second ethylene polymer in a second reactor by polymerizing ethylene in the presence of a second single site catalyst system and forming a third ethylene polymer in a third reactor by polymerizing ethylene in the presence of a third single site catalyst system.

[0134] In an embodiment, the ethylene polymer product of the present disclosure is made in-situ by forming a first ethylene polymer in a first reactor by polymerizing ethylene in the presence of a first single site catalyst system; forming a second ethylene polymer in a second reactor by polymerizing ethylene in the presence of a second single site catalyst system and forming a third ethylene polymer in a third reactor by polymerizing ethylene in the presence of a multi-site catalyst system.

[0135] In an embodiment, the ethylene polymer product of the present disclosure is made in-situ by forming a first ethylene polymer in a first reactor by polymerizing ethylene in the presence of a first single site catalyst system; forming a second ethylene polymer in a second reactor by polymerizing ethylene in the presence of a second single site catalyst system and forming a third ethylene polymer in a third reactor by polymerizing ethylene in the presence of a Ziegler-Natta catalyst system.

[0136] It is also contemplated by the present disclosure, that the ethylene polymer product of the present disclosure is made ex-situ by melt blending or solution blending two different components i) and ii); namely: i) a bimodal polyethylene blend comprising a first ethylene polymer and a second ethylene polymer; and ii) a third ethylene polymer.

[0137] In an embodiment, the bimodal polyethylene blend is made in-situ by forming a first ethylene polymer in a first reactor by polymerizing ethylene in the presence of a first single site catalyst system; and forming a second ethylene polymer in a second reactor by polymerizing ethylene in the presence of a second single site catalyst system.

[0138] In an embodiment, the bimodal polyethylene blend is made in-situ by forming a first ethylene polymer in a first solution-phase polymerization reactor by polymerizing ethylene in the presence of a first single site catalyst system; and forming a second ethylene polymerin a second solution-phase polymerization reactor by polymerizing ethylene in the presence of a second single site catalyst system.

[0139] In an embodiment, the bimodal polyethylene blend is made in-situ by forming a first ethylene polymer in a first solution-phase polymerization reactor by polymerizing ethylene in the presence of a first single site catalyst system; and forming a second ethylene polymer in a second solution-phase polymerization reactor by polymerizing ethylene in the presence of a second single site catalyst system, where the first solution-phase polymerization reactor and the second solution-phase polymerization reactor are configured in series with one another.

[0140] In an embodiment, the bimodal polyethylene blend is made in-situ by forming a first ethylene polymer in a first solution-phase polymerization reactor by polymerizing ethylene in the presence of a first single site catalyst system; and forming a second ethylene polymer in a second solution-phase polymerization reactor by polymerizing ethylene in the presence of a second single site catalyst system, where the first solution-phase polymerization reactor and the second solution-phase polymerization reactor are configured in parallel with one another.

[0141] In an embodiment of the disclosure, the first single site catalyst system and the second single site catalyst system are independently chosen, and each comprise an unbridged phosphinimine catalyst.

[0142] In and embodiment of the disclosure, the first single site catalyst system and the second single site catalyst system are independently chosen, and each comprise an unbridged phosphinimine catalyst represented by formula:

[0143] (LA)aM(PI)b(Q)n

[0144] wherein (LA) represents is cyclopentadienyl-type ligand; M represents a metal atom selected from the group consisting of Ti, Zr, and Hf; PI represents a phosphinimine ligand; Q represents an activatable ligand; a is 0 or 1; b is 1 or 2; (a+b) = 2; n is 1 or 2, and; the sum of (a+b+n) equals the valance of the metal M.

[0145] As used herein, the term “cyclopentadienyl-type” ligand is meant to include ligands which contain at least one five-carbon ring which is bonded to the metal via eta-5 (or in some cases eta-3) bonding. Thus, the term “cyclopentadienyl-type” includes, for example, unsubstituted cyclopentadienyl, singly or multiply substituted cyclopentadienyl, unsubstituted indenyl, singly or multiply substituted indenyl, unsubstituted fluorenyl and singly or multiply substituted fluorenyl. Hydrogenated versions of indenyl and fluorenyl ligands are also contemplated for use in the current disclosure, so long as the five-carbonring which bonds to the metal via eta-5 (or in some cases eta-3) bonding remains intact. Substituents for a cyclopentadienyl ligand, an indenyl ligand (or hydrogenated version thereof) and a fluorenyl ligand (or hydrogenated version thereof) may be selected from the group consisting of a C1-30 hydrocarbyl radical (which hydrocarbyl radical may be unsubstituted or further substituted by for example a halide and / or a hydrocarbyl group; for example a suitable substituted C1-30 hydrocarbyl radical is a pentafluorobenzyl group such as -CH2C6F5); a halogen atom; a C1-8 alkoxy radical; a C6-10 aryl or aryloxy radical (each of which may be further substituted by for example a halide and / or a hydrocarbyl group); an amido radical which is unsubstituted or substituted by up to two C1-8 alkyl radicals; a phosphido radical which is unsubstituted or substituted by up to two C1-8 alkyl radicals; a silyl radical of the formula -Si(R')3 wherein each R' is independently selected from the group consisting of hydrogen, a C1-8 alkyl or alkoxy radical, C6-10 aryl or aryloxy radicals; and a germanyl radical of the formula -Ge(R')3 wherein R' is as defined directly above.

[0146] The phosphinimine ligand, PI, is defined by formula:

[0147] (RP)3P = N -wherein the Rpgroups are independently selected from: a hydrogen atom; a halogen atom; C1-20 hydrocarbyl radicals which are unsubstituted or substituted with one or more halogen atom(s); a C1-8 alkoxy radical; a C6-10 aryl radical; a C6-10 aryloxy radical; an amido radical; a silyl radical of formula -Si(Rs)3, wherein the Rs groups are independently selected from, a hydrogen atom, a C1-8 alkyl or alkoxy radical, a C6-10 aryl radical, a C6-10 aryloxy radical, or a germanyl radical of formula -Ge(RG)3, wherein the RGgroups are defined as Rsis defined in this paragraph.

[0148] In some embodiment of the disclosure, the metal, M in the unbridged phosphinimine catalyst is titanium, Ti.

[0149] In some embodiments, the first single site catalyst system, and the second single site catalyst system, both comprise the same unbridged phosphinimine catalyst.

[0150] In some embodiments, the first single site catalyst system, and the second single site catalyst system, both comprise cyclopentadienyl tri(tertiarybutyl)phosphinimine titanium dichloride, Cp((t-Bu)3PN)TiCh.

[0151] In addition to the single site catalyst molecule per se (e.g., the unbridged phosphinimine catalyst), an active single site catalyst system may further comprise one or more than one catalyst activator (also known as a “co-catalysf ’) used to activate the prepolymerization catalyst and which can be any suitable catalyst activator (or co-catalyst)known to persons skilled in the art, including one or more catalyst activator(s) selected from the group consisting of the so-called ionic activators, which includes boron-based activators; and alkylaluminoxanes.

[0152] Although the exact structure of alkylaluminoxane is uncertain, subject matter experts generally agree that it is an oligomeric species that contain repeating units of the general formula:

[0153] (R)2A1O-(A1(R)-O)n-A1(R)2

[0154] where the R groups may be the same or different linear, branched or cyclic hydrocarbyl radicals containing 1 to 20 carbon atoms and n is from 0 to about 50. A non-limiting example of an alkylaluminoxane is methylaluminoxane (or MAO) wherein each R group is a methyl radical.

[0155] In an embodiment of the disclosure, R of the alkylaluminoxane, is a methyl radical and m is from 10 to 40.

[0156] In an embodiment of the disclosure, the co-catalyst is modified methylaluminoxane (MMAO).

[0157] It is well known in the art, that the alkylaluminoxane can serve dual roles as both an alkylator and an activator. Hence, an alkylaluminoxane co-catalyst is often used in combination with activatable ligands such as halogens.

[0158] In general, ionic activators are comprised of a cation and a bulky anion; wherein the latter is substantially non-coordinating. Non-limiting examples of ionic activators are boron ionic activators that are four coordinate with four ligands bonded to the boron atom. Nonlimiting examples of boron ionic activators include the following formulas shown below:

[0159] [R5]+[B(R7)4]-where B represents a boron atom, R5is an aromatic hydrocarbyl (e.g., triphenyl methyl cation) and each R7is independently selected from phenyl radicals which are unsubstituted or substituted with from 3 to 5 substituents selected from fluorine atoms, Ci-4 alkyl or alkoxy radicals which are unsubstituted or substituted by fluorine atoms; and a silyl radical of formula -Si(R9)3, where each R9is independently selected from hydrogen atoms and Ci-4 alkyl radicals, and

[0160] [(R8)tZH]+[B(R7)4]“

[0161] where B is a boron atom, H is a hydrogen atom, Z is a nitrogen or phosphorus atom, t is 2 or 3 and R8is selected from Ci-s alkyl radicals, phenyl radicals which are unsubstituted or substituted by up to three Ci-4 alkyl radicals, or one R8taken together with the nitrogen atom may form an anilinium radical and R7is as defined above.In both formulas, a non-limiting example of R7is a pentafluorophenyl radical. In general, boron ionic activators may be described as salts of tetra(perfluorophenyl) boron; non-limiting examples include anilinium, carbonium, oxonium, phosphonium and sulfonium salts of tetra(perfluorophenyl)boron with anilinium and trityl (or triphenylmethylium). Additional non-limiting examples of ionic activators include: triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(m,m-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boron, N, N-dimethylanilinium tetra(phenyl)boron, N, N-diethylanilinium tetra(phenyl)boron, N, N-diethylanilinium tetra(phenyl)n-butylboron, N, N-2,4,6-pentamethylanilinium tetra(phenyl)boron, di-(isopropyl)ammonium tetra(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boron, triphenylphosphonium tetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron, tri(dimethylphenyl)phosphonium tetra(phenyl)boron, tropillium tetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl borate, benzene(diazonium)tetrakispentafluorophenyl borate, tropillium tetrakis(2, 3,5,6-tetrafluorophenyl)borate, triphenylmethylium tetrakis(2,3,5,6-tetrafluorophenyl)borate, benzene(diazonium) tetrakis(3,4,5-trifluorophenyl)borate, tropillium tetrakis(3,4,5 -trifluorophenyl)borate, benzene(di azonium) tetrakis(3,4,5-trifluorophenyl)borate, tropillium tetrakis(l,2,2-trifluoroethenyl)borate, triphenylmethylium tetrakis(l,2,2-trifluoroethenyl)borate, benzene(diazonium) tetrakis(l,2,2-trifluoroethenyl)borate, tropillium tetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylmethylium tetraki s(2, 3,4,5 -tetrafluorophenyl)borate, and benzene(di azonium) tetrakis(2,3,4,5 tetrafluorophenyl)borate. Readily available commercial ionic activators include N, N-dimethylanilinium tetrakispentafluorophenyl borate, and triphenylmethylium tetrakispentafluorophenyl borate.

[0162] The active single site catalyst system may in some embodiments further comprise a hindered phenol compound. Non-limiting example of hindered phenols include butylated phenolic antioxidants, butylated hydroxytoluene, 2,6-di-tertiarybutyl-4-ethyl phenol, 4,4'-methylenebis (2,6-di-tertiary-butylphenol), 1,3, 5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene and octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate.To produce an active singe catalyst system the quantity and mole ratios of the three or four components: the first homogenous catalyst, the alkylaluminoxane, the ionic activator, and the optional hindered phenol are optimized.

[0163] In an embodiment, the solution phase polymerization reactor used as a first solutionphase reactor and a second solution-phase reactor is a continuously stirred tank reactor.

[0164] In a solution phase polymerization reactor, a variety of solvents may be used as the process solvent; non-limiting examples include linear, branched or cyclic Cs to C12 alkanes. Suitable catalyst component solvents include aliphatic and aromatic hydrocarbons. Nonlimiting examples of aliphatic catalyst component solvents include linear, branched or cyclic C5-12 aliphatic hydrocarbons, e.g. pentane, methyl pentane, hexane, heptane, octane, cyclohexane, cyclopentane, methylcyclohexane, hydrogenated naphtha or combinations thereof. Non-limiting examples of aromatic catalyst component solvents include benzene, toluene (methylbenzene), ethylbenzene, o-xylene (1,2-dimethylbenzene), m-xylene (1,3-dimethylbenzene), p-xylene (1,4-dimethylbenzene), mixtures of xylene isomers, hemellitene (1,2, 3 -trimethylbenzene), pseudocumene (1,2,4-trimethylbenzene), mesitylene (1,3,5-trimethylbenzene), mixtures of trimethylbenzene isomers, prehenitene (1, 2,3,4-tetramethylbenzene), durene (1,2,3,5-tetramethylbenzene), mixtures of tetramethylbenzene isomers, pentamethylbenzene, hexamethylbenzene and combinations thereof.

[0165] In an embodiment, the bimodal polyethylene blend is recovered from the polymerization process and is then passed into an extruder for being melt blended with a third ethylene polymer and additives to produce the ethylene polymer product.

[0166] In an embodiment, the bimodal polyethylene blend is recovered from the polymerization process, passed into an extruder, blended with antioxidants and a nucleating agent, cooled, and pelletized to create an intermediate product referred to as the “formulated” bimodal polyethylene blend. This formulated bimodal blend is then remelted and combined with a third ethylene polymer and optional anti -blocking additive (e.g., talc powder) to produce the “final” ethylene polymer product.

[0167] In embodiments of the disclosure, the ethylene polymer product has a density which may be greater than about 0.950, or greater than about 0.955, or greater than about 0.96, or greater than about 0.965. In embodiments of the disclosure, the ethylene polymer product has a density or from about 0.94 g / cm3to about 0.985 g / cm3, or from about 0.945 g / cm3to 0.982 g / cm3, or from about 0.95 g / cm3to about 0.980 g / cm3, or from about 0.95 g / cm3to about 0.978 g / cm3, or from about 0.95 g / cm3to about 0.975 g / cm3, or from about 0.95 g / cm3to about 0.970 g / cm3.In embodiments of the disclosure, the melt index I2 of the ethylene polymer product may be from about 0.01 dg / min to about 1000 dg / min, or from about 0.01 dg / min to about 500 dg / min, or from about 0.01 dg / min to about 100 dg / min, or from about 0.01 dg / min to about 50 dg / min, or from about 0.01 dg / min to about 25 dg / min, or from about 0.01 dg / min to about 15 dg / min, or from about 0.1 dg / min to about 15 dg / min, or from about 0.3 dg / min to about 15 dg / min, or from about 0.5 dg / min to about 15 dg / min, or from about 0.5 dg / min to about 10 dg / min, or from about 0.5 dg / min to about 5 dg / min, or from about 0.5 dg / min to about 3 dg / min, or from about 0.5 dg / min to about 2.5 dg / min.

[0168] In embodiments of the disclosure, the ethylene polymer product, comprises: A) a bimodal polyethylene blend; and B) from about 0.1×104parts per million to about 5×104parts per million of a third ethylene polymer, based on the total weight of the bimodal polyethylene blend. In these embodiments, the bimodal polyethylene blend consisting essentially of: a first ethylene polymer having a first weight-average molecular weight, Mw,1, of from about 50 kg / mol to about 250 kg / mol, a first poly dispersity index, Mw,1 / Mn,1, of from about 1.7 to about 2.5, and a first density ρ1 of greater than about 0.94 g / cm3; and a second ethylene polymer having a second weight-average molecular weight, v,2, of from about 8 kg / mol to about 30 kg / mol, a second poly dispersity index, v,2 / Mn,2, of from about 1.7 to about 2.5, and a second density pi of greater than about 0.95 g / cm3. In these embodiments, the third ethylene polymer has a melting point of greater than 110°C, as determined by differential scanning calorimetry; and a third weight-average molecular weight, V,3, satisfying the inequality v, 3 < A / w,2.

[0169] In embodiments of the disclosure, the ethylene polymer product, comprises: A) a bimodal polyethylene blend; and B) from about 0.1×104parts per million to about 5×104parts per million of a third ethylene polymer, based on the total weight of the bimodal polyethylene blend. In these embodiments, the bimodal polyethylene blend consisting essentially of: a first ethylene polymer having a first weight-average molecular weight, Mw,1, of from about 50 kg / mol to about 250 kg / mol, a first poly dispersity index, Mw,1 / Mn,1, of from about 1.7 to about 2.5, and a first density pi of greater than about 0.94 g / cm3; and a second ethylene polymer having a second weight-average molecular weight, v,2, of from about 8 kg / mol to about 30 kg / mol, a second poly dispersity index, v,2 / Mn,2, of from about 1.7 to about 2.5, and a second density pi of greater than about 0.95 g / cm3. In these embodiments, the third ethylene polymer has a melting point of greater than 110°C, as determined by differential scanning calorimetry; a heat of fusion of greater than 200 J / g, asdetermined by differential scanning calorimetry; and a third weight-average molecular weight, V,3, satisfying the inequality v, 3 < M

[0170] Additives

[0171] In embodiments of disclosure, the final ethylene polymer product comprises from about 1 x 102parts per million to about 3×103parts per million of a nucleating agent, based on the total weight of the bimodal polyethylene blend. The term “nucleating agent”, as used herein, is meant to convey its conventional meaning to those skilled in the art of preparing nucleated semicrystalline polymers, namely an additive that changes the crystallization behavior of semicrystalline polymers as they are cooled from a molten state. It will be readily appreciated by those skilled in the art that some care must be taken to ensure that the nucleating agent is well dispersed.

[0172] In the present disclosure, organic nucleating agents which have a very high melting point are preferred. These nucleating agents remain solid when applied in ethylene polymers and are sometimes referred to as “insoluble organic” nucleating agents to indicate that they do not melt disperse in polyethylene during the extrusion operations. In general, these insoluble organic nucleating agents either do not have a true melting point (i.e., they decompose prior to melting) or have a melting point greater than 300°C, or, alternatively stated, a melting / decomposition temperature of greater than 300°C.

[0173] Non-limiting examples of suitable nucleating agents include the cyclic organic structures and salts thereof as disclosed in U. S. Pat. No. 5,981,636, U. S. Pat. No. 5,981,636 and U. S. Pat. No. 6,465,551; the salts of certain cyclic dicarboxylic acids having a hexahydrophtalic acid structure (or “HHPA” structure) as disclosed in U. S. Pat. No.

[0174] 6,559,971, U. S. Pat. No. 6,559,971 and U. S. Pat. No. 6,559,971; phosphate esters, such as those disclosed in U. S. Pat. No. 5,342,868; phosphonic acids, such as those disclosed in U. S. Pat. No. 12,037,478; and benzoic acids, such as those disclosed in U. S. Pat. App. Pub. No. 2015 / 0086736, U. S. Pat. No. 9,120,914, U. S. Pat. No. 9, 193,845 and U. S. Pat. No. 9,200,144.

[0175] In some embodiments, the nucleating agent comprises disodium bicyclo [2.2.1] heptene dicarboxylate (CAS registry number 351870-33-2, commercially available as HYPERFORM® HPN 68L from Milliken).

[0176] In some embodiments, the nucleating agent comprises a calcium salt of 1,2-cyclohexanedicarboxylic acid (CAS registry number 491589-22-1, commercially available as HYPERFORM® HPN20E from Milliken).In some embodiments, the nucleating agent comprises sodium 2,2’ -methylene bis-(4,6-di-tert-butylphenyl) phosphate (CAS registry number 85209-91-2, commercially available as IRGASTAB® NA11 from BASF).

[0177] In some embodiments, the nucleating agent comprises calcium tert-butylphosphonate (CAS registry number 81607-35-4).

[0178] In some embodiments, the nucleating agent comprises sodium 4-chlorophenylamido-benzoate (CAS registry number 1489170-67-3, commercially available as HYPERFORM® HPN 20M from Milliken).

[0179] In embodiments of the disclosure, the ethylene polymer product comprises from about 5×102parts per million to about 1×104parts per million of an inorganic anti-blocking additive, based on the total weight of the bimodal polyethylene blend. Inorganic antiblocking additives are well known to those of ordinary skill in the art. Non-limiting examples of inorganic anti-blocking additives include talc, diatomaceous earth, synthetic silica, kaolin, calcium carbonate, ceramic microspheres (such as those sold under the trademark ZEEOSPHERES™ by 3M). As used herein, the term “anti-blocking additive” refers to any substance that reduces unwanted tendency of film layers to adhere to each other or to other surfaces (e.g., processing equipment). While not wishing to be limited by any single theory, larger particle size inorganic anti -blocking additives are typically known for their higher blocking resistance. However, these larger particles are often more challenging to disperse, which can lead to the formation of agglomerates. These agglomerates may reduce the barrier performance and affect the physical and optical properties of the films prepared from the ethylene polymer product of the present disclosure. As a person of ordinary skill in the art would understand, managing the particle size distribution of the inorganic anti -blocking additive, particularly the content of larger particles, can balance the barrier, physical, optical and anti-blocking properties.

[0180] In some embodiments, the ethylene polymer product comprises from about 5×102parts per million to about 1 x 104parts per million of talc, based on the total weight of the bimodal polyethylene blend. Those commercially available talcs which are used as antiblocking additives are preferred for use in the present disclosure. A suitable example is POLYBLOC™, available from Mineral Technologies.

[0181] The ethylene polymer product may also contain other conventional additives, especially primary antioxidants (such as hindered phenols, including vitamin E); (2) secondary antioxidants (especially phosphites and phosphonites); and (3) process aids (especially fluoroelastomer and / or polyethylene glycol process aid).Flexible Manufactured Articles

[0182] The ethylene polymer product disclosed herein may be converted into flexible manufactured articles such as monolayer or multilayer films, such films are well known to those experienced in the art.

[0183] Non-limiting examples of processes to prepare such films include blown film process. In the blown film extrusion process, an extruder heats, melts, mixes and conveys a thermoplastic, or a thermoplastic blend. Once molten, the thermoplastic is forced through an annular die to produce a thermoplastic tube. In the case of co-extrusion, multiple extruders are employed to produce a multilayer thermoplastic tube. The temperature of the extrusion process is primarily determined by the thermoplastic or thermoplastic blend being processed, for example the melting temperature or glass transition temperature of the thermoplastic and the desired viscosity of the melt. In the case of polyolefins, typical extrusion temperatures are from 330°F to 550°F (166°C to 288°C). Upon exit from the annular die, the thermoplastic tube is inflated with air, cooled, solidified and pulled through a pair of nip rollers. Due to air inflation, the tube increases in diameter forming a bubble of desired size. Due to the pulling action of the nip rollers the bubble is stretched in the machine direction. Thus, the bubble is stretched in two directions: the transverse direction (TD) where the inflating air increases the diameter of the bubble; and the machine direction (MD) where the nip rollers stretch the bubble. As a result, the physical properties of blown films are typically anisotropic, i.e. the physical properties differ in the MD and TD directions; for example, film tear strength and tensile properties typically differ in the MD and TD. In some prior art documents, the terms “cross direction” or “CD” is used; these terms are equivalent to the terms “transverse direction” or “TD” used in this disclosure. In the blown film process, air is also blown on the external bubble circumference to cool the thermoplastic as it exits the annular die. The final width of the film is determined by controlling the inflating air or the internal bubble pressure; in other words, increasing or decreasing bubble diameter. Film thickness is controlled primarily by increasing or decreasing the speed of the nip rollers to control the draw-down rate. After exiting the nip rollers, the bubble or tube is collapsed and may be slit in the machine direction thus creating sheeting. Each sheet may be wound into a roll of film. Each roll may be further slit to create film of the desired width.

[0184] Another example of a process to prepare films includes cast film processes. The cast film process is similar in that a single or multiple extruders may be used; however, the various thermoplastic materials are metered into a flat die and extruded into a multilayersheet, rather than a tube. In the cast film process, films are extruded from a flat die onto a chilled roll or a nipped roll, optionally, with a vacuum box and / or air-knife.

[0185] Depending on the end-use application, the disclosed ethylene polymer product may be converted into films that span a wide range of thicknesses. Non-limiting examples include food packaging films where thicknesses may range from about 0.5 mil (~13 pm) to about 4 mil (-102 pm); and in heavy duty sack applications film thickness may range from about 2 mil (-51pm) to about 10 mil (254 pm).

[0186] The ethylene polymer product disclosed herein may be used in monolayer films; where the monolayer may contain more than one ethylene polymer product as disclosed herein and / or additional polymers; non-limiting examples of additional polymers include polyethylene polymers and propylene polymers. The lower limit on the weight percent of the ethylene polymer product in a monolayer film may be about 3 wt.%, in other cases about 10 wt.% and in still other cases about 30 wt.%. The upper limit on the weight percent of the ethylene polymer product in the monolayer film may be 100 wt.%, in other cases about 90 wt.% and in still other cases about 70 wt.%.

[0187] In some embodiments, a film layer comprising the ethylene polymer product of the present disclosure has a normalized water vapor transmission rate, nWVTR, of 0.10 g / 100 in2 / day or less at a film thickness of about 1.5 mil. The normalized water vapor transmission rate is determined by multiplying the experimentally measured WVTR at 38°C and a relative humidity of 100% by the actual film thickness in mils and subsequently dividing the result by 1.5 mils — i.e., nWVTR = (actual WVTR) x (actual thickness in mils) / (target thickness in mils) with the target thickness = 1.5 mil.

[0188] In some embodiments, a film layer comprising the ethylene polymer product of the present disclosure layer has a normalized oxygen transmission rate, nOTR, of 30 cm3 / 100 in2 / day or less at a film thickness of about 1.5 mil, wherein the normalized oxygen transmission rate is determined by multiplying the experimentally measured OTR at 23°C and at a relative humidity of 0% by the actual film thickness in mils and subsequently dividing the result by 1.5 mils — i.e., nOTR = (actual OTR) x (actual thickness in mils) / (target thickness in mils) with the target thickness = 1.5 mil.

[0189] In some embodiments, a film layer comprises an ethylene polymer product, the ethylene polymer product comprising: A) a bimodal polyethylene blend; and B) from about 1×102parts per million to about 1×105parts per million of a third ethylene polymer, based on the total weight of the bimodal polyethylene blend. The bimodal polyethylene blend comprises from about 30 weight percent to about 70 weight percent, based on the totalweight of the bimodal polyethylene blend, of a first ethylene polymer having a first weightaverage molecular weight, v,i, of from about 50 kg / mol to about 250 kg / mol, a first poly dispersity index, A / W,i / Mn,i, of from about 1.7 to about 2.5, and a first density ρ1 of greater than about 0.94 g / cm3; and from about 70 weight percent to about 30 weight percent, based on the total weight of the bimodal polyethylene blend, of a second ethylene polymer having a second weight-average molecular weight, v,2, of from about 8 kg / mol to about 30 kg / mol, a second poly dispersity index, v,2 / Mn,2, of from about 1.7 to about 2.5, and a second density pi of greater than about 0.95 g / cm3. The third ethylene polymer has a melting point of greater than 80°C, as determined by differential scanning calorimetry; and a third weight-average molecular weight, v,3, satisfying the inequality v,3 < v,2.

[0190] In some embodiments of the film layer, the third ethylene polymer has a heat of fusion of greater than 200 J / g and a melting point of greater than 110°C, as determined by differential scanning calorimetry.

[0191] In some embodiments of the film layer, the third ethylene polymer has a third poly dispersity index, Mw,3 / Mn,3, of from greater than 1 to less than about 3.

[0192] In some embodiments of the film layer, the third ethylene polymer contains greater than about 70 weight percent, based on the total weight of the third ethylene polymer, of material having a molecular weight of greater than 1,000 g / mol and less than 10,000 g / mol.

[0193] In some embodiments of the film layer, the bimodal polyethylene blend is further characterized by at least one of the following features: (I) a poly dispersity index, AAM, of from about 4 to about 18; (II) a z-average molecular weight to number-average molecular weight ratio, Mz / Mn, of from about 8 to about 40; (III) a z-average molecular weight to weight-average molecular weight ratio, Mz / Mw, of from about 2 to about 5; (IV) a number-average molecular weight, Mn, of from about 5 kg / mol to about 25 kg / mol; (V) a weight-average molecular weight, Mw, of from about 60 kg / mol to about 180 kg / mol; and (VI) a z-average molecular weight, Mz, of from about 180 kg / mol to about 350 kg / mol.

[0194] In some embodiments of the film layer, the bimodal polyethylene blend is an in-situ blend. As used herein, the term “in-situ” refers to a process in which the ethylene polymer product is formed while polymerization is occurring and is herein distinguished from a physical “ex-situ” process.

[0195] In some embodiments of the film layer, the first ethylene polymer, the second ethylene polymer and the third ethylene polymer are each an ethylene homopolymer. In these embodiments, the term “ethylene homopolymer” is meant to convey a conventional meaning — i.e., the first ethylene polymer, the second ethylene polymer and the thirdethylene polymer each essentially consists of ethylene monomer units. Those of ordinary skill in the art recognize that very minor amounts — e.g., less than 0.5 mol% — of a-olefinic comonomer units may be present in the “ethylene homopolymer” as a result of contamination of the ethylene stream and / or the polymerization medium.

[0196] In some embodiments of the film layer, the ethylene polymer product has an overall density of greater than about 0.950 g / cm3and an overall melt index I2 of from about 0.5 g / 10 minute to about 15 g / 10 minute.

[0197] In some embodiments of the film layer, the film layer is a blown film layer.

[0198] In some embodiments of the blown film layer, the film layer has a normalized water vapor transmission rate, nWVTR, of 0.10 g / 100 in2 / day or less at a film thickness of about 1.5 mil, wherein the normalized water vapor transmission rate is determined by multiplying the experimentally measured WVTR at 38°C and a relative humidity of 100% by the actual film thickness in mils and subsequently dividing the result by 1.5 mils.

[0199] In some embodiments of the blown film layer, the film layer has a normalized water vapor transmission rate, nWVTR, of 0.10 g / 100 in2 / day or less at a film thickness of about 1.5 mil, and the ethylene polymer product comprises: C) from about 1 x 102parts per million to about 3×103parts per million of a nucleating agent, based on the total weight of the bimodal polyethylene blend; and D) from about 5×102parts per million to about 1 x 104parts per million of an inorganic anti-blocking additive, based on the total weight of the bimodal polyethylene blend. In these embodiments, the nucleating agent in C) may comprise a calcium salt of 1,2-cyclohexanedicarboxylic acid. In these embodiments, the inorganic antiblocking additive in D) may comprise talc.

[0200] In some embodiments of the blown film layer, the film layer has a normalized oxygen transmission rate, nOTR, of 30 cm3 / 100 in2 / day or less at a film thickness of about 1.5 mil, wherein the normalized oxygen transmission rate is determined by multiplying the experimentally measured OTR at 23 °C and at a relative humidity of 0% by the actual film thickness in mils and subsequently dividing the result by 1.5 mils.

[0201] In some embodiments of the blown film layer, the film layer has a normalized oxygen transmission rate, nOTR, of 30 cm3 / 100 in2 / day or less at a film thickness of about 1.5 mil. In these embodiments, the ethylene polymer product comprises: C’) from about 1 x 102parts per million to about 3 x 103parts per million of a nucleating agent, based on the total weight of the bimodal polyethylene blend; and D’) from about 5×102parts per million to about 1×104parts per million of an inorganic anti-blocking additive, based on the total weight of the bimodal polyethylene blend. In these embodiments, the nucleating agent inC’) may comprise a calcium salt of 1,2-cyclohexanedicarboxylic acid. In these embodiments, the inorganic anti-blocking additive in D’) may comprise talc.

[0202] The ethylene polymer product disclosed herein may also be used in one or more layers of a multilayer film; non-limiting examples of multilayer films include three, five, seven, nine, eleven or more layers. Non-limiting examples of processes to prepare multilayer film structures include blown film co-extrusion processes and cast co-extrusion processes. Further examples of processes to prepare multilayer film structures include laminations and coatings, wherein a multilayer film structure is extrusion laminated or adhesively laminated or extrusion coated.

[0203] The thickness of a specific layer (containing the ethylene polymer product) within a multilayer film structure may be about 5%, in other cases about 15% and in still other cases about 30% of the total multilayer film thickness. In other embodiments, the thickness of a specific layer (containing the ethylene polymer product) within a multilayer film may be about 95%, in other cases about 80% and in still other cases about 65% of the total multilayer film thickness. Each individual layer of a multilayer film may contain more than one ethylene polymer product and / or additional polymer(s).

[0204] In some embodiments of the multilayer structure, the film layer comprising the ethylene polymer product — or at least one film layer comprising the ethylene polymer product if there is more than one layer containing the ethylene polymer product — is a skin layer of the multilayer film structure.

[0205] In some embodiments, a multilayer film structure comprises at least one skin layer comprising an ethylene polymer product. In these embodiments, the ethylene polymer product comprises A’) a bimodal polyethylene blend; B’) from about 1×102parts per million to about 1×105parts per million of a third ethylene polymer, based on the total weight of the bimodal polyethylene blend; C”) from about 1 x 102parts per million to about 3 x 103parts per million of a nucleating agent, based on the total weight of the bimodal polyethylene blend; and D”) from about 5×102parts per million to about 1 x 104parts per million of an inorganic anti-blocking additive, based on the total weight of the bimodal polyethylene blend. In these embodiments, the bimodal polyethylene blend in A’) comprises from about 30 weight percent to about 70 weight percent, based on the total weight of the bimodal polyethylene blend, of a first ethylene polymer having a first weight-average molecular weight, Mw,1, of from about 50 kg / mol to about 250 kg / mol, a first poly dispersity index, Mw,1 / Mn,1, of from about 1.7 to about 2.5, and a first density ρ1 of greater than about 0.94 g / cm3; and from about 70 weight percent to about 30 weight percent, based on the totalweight of the bimodal polyethylene blend, of a second ethylene polymer having a second weight-average molecular weight, fw,2, of from about 8 kg / mol to about 30 kg / mol, a second poly dispersity index, A / W,2 / Mn,2, of from about 1.7 to about 2.5, and a second density pi of greater than about 0.95 g / cm3. In these embodiments, the third ethylene polymer in B’) has a melting point of greater than 80°C, as determined by differential scanning calorimetry; and a third weight-average molecular weight, fw,3, satisfying the inequality A / w,3 < v,2.

[0206] In some embodiments of the multilayer film, the nucleating agent in C”) comprises a calcium salt of 1,2-cyclohexanedicarboxylic acid.

[0207] In some embodiments of the multilayer film, the inorganic anti-blocking additive in D”) comprises talc.

[0208] In some embodiments of the multilayer film, the third ethylene polymer in B’) has a heat of fusion of greater than 200 J / g and a melting point of greater than 110°C, as determined by differential scanning calorimetry.

[0209] In some embodiments of the multilayer film, the third ethylene polymer in B’) has a third poly dispersity index, v,3 / Mn,3, of from greater than 1 to less than about 3.

[0210] In some embodiments of the multilayer film, the third ethylene polymer in B’) contains greater than about 70 weight percent, based on the total weight of the third ethylene polymer, of material having a molecular weight of greater than 1,000 g / mol and less than 10,000 g / mol.

[0211] In some embodiments of the multilayer film, the bimodal polyethylene blend in A’) is further characterized by at least one of the following features: (I) a poly dispersity index, v / A7n, of from about 4 to about 18; (II) a z-average molecular weight to number-average molecular weight ratio, Mz / Mn, of from about 8 to about 40; (III) a z-average molecular weight to weight-average molecular weight ratio, A7z / , of from about 2 to about 5; (IV) a number-average molecular weight, A n, of from about 5 kg / mol to about 25 kg / mol; (V) a weight-average molecular weight, A / w, of from about 60 kg / mol to about 180 kg / mol; and (VI) a z-average molecular weight, fz, of from about 180 kg / mol to about 350 kg / mol.

[0212] In some embodiments of the multilayer film, the bimodal polyethylene blend in A’) is an in-situ blend. As used herein, the term “in-situ” refers to a process in which the ethylene polymer product is formed while polymerization is occurring and is herein distinguished from a physical “ex-situ” process.

[0213] In some embodiments of the multilayer film, the first ethylene polymer, the second ethylene polymer and the third ethylene polymer, in A’) and B’), are each an ethylene homopolymer. In these embodiments, the term “ethylene homopolymer” is meant to conveya conventional meaning — i.e., the first ethylene polymer, the second ethylene polymer and the third ethylene polymer each essentially consists of ethylene monomer units. Those of ordinary skill in the art recognize that very minor amounts — e.g., less than 0.5 mol% — of a-olefinic comonomer units may be present in the “ethylene homopolymer” as a result of contamination of the ethylene stream and / or the polymerization medium.

[0214] In some embodiments of the multilayer film, the ethylene polymer product has an overall density of greater than about 0.950 g / cm3and an overall melt index I2 of from about 0.5 g / 10 minute to about 15 g / 10 minute.

[0215] The following examples are presented for the purpose of illustrating selected embodiments of this disclosure; it being understood that the examples presented do not limit the claims presented.

[0216] EXAMPLES

[0217] Testing Methods

[0218] Prior to testing, each specimen was conditioned for at least 24 hours at 23 ±2°C and 50 ±10% relative humidity and subsequent testing was conducted at 23 ±2°C and 50 ±10% relative humidity. Herein, the term “ASTM conditions” refers to a laboratory that is maintained at 23 ±2°C and 50 ±10% relative humidity; and specimens to be tested were conditioned for at least 24 hours in this laboratory prior to testing. ASTM refers to the American Society for Testing and Materials.

[0219] Density

[0220] Density was determined using ASTM D792-13 (November 1, 2013).

[0221] Melt Index

[0222] Melt index was determined using ASTM D1238 (August 1, 2013). Melt indexes, I2, 16, 110 and I21 were measured at 190°C, using weights of 2.16 kg, 6.48 kg, 10 kg and a 21.6 kg respectively. Herein, the term “stress exponent” or its acronym “S. Ex ”, is defined by the following relationship: S. Ex.= log (Ie / l2) / log (6480 / 2160); wherein E and I2 are the melt flow rates measured at 190°C using 6.48 kg and 2.16 kg loads, respectively.

[0223] Conventional Gel Permeation Chromatography (GPC)

[0224] A polymer sample (about 15 mg) was weighed into the sample vial and loaded onto the auto-sampler of the Polymer Char GPC-IR5 unit. The vail was filled with 8 ml 1,2,4-tri chlorobenzene (TCB), heated to the desired dissolution temperature (e.g., 160°C) with a shaking for 120 minutes. The antioxidant 2,6-di-tert-butyl-4-methylphenol (BHT) was added to TCB in order to stabilize the polymer against oxidative degradation. The BHT concentration was 250 ppm. Sample solutions were chromatographed at 140°C on aPolymer Char GPC-IR5 chromatography unit equipped with four Shodex GPC columns (HT803, HT804, HT805 and HT806) using TCB as the mobile phase with a flow rate of 1.0 mL / minute, with an Infrared IR5 as the concentration detector. BHT was added to the mobile phase at a concentration of 250 ppm to protect GPC columns from oxidative degradation. The sample injection volume was 200 pL. The GPC columns were calibrated with narrow distribution polystyrene standards. The polystyrene molecular weights were converted to polyethylene molecular weights using the Mark-Houwink equation, as described in the ASTM standard test method D6474. The GPC raw data were processed with Excel spreadsheet, to produce molar mass averages (Mn, Mw, Mz) and molar mass distribution (e.g., poly dispersity, Mw / Mn). The weight percent of material having a molecular weight of greater than 1,000 g / mol and less than 10,000 g / mol was determined by summing the weight fraction of GPC fractions which had a molecular weight (MW) of greater than 1,000 g / mol and less than 10,000 g / mol in the conventional GPC experiment. In the polyethylene art, a commonly used term that is equivalent to GPC is SEC, i.e., size exclusion chromatography.

[0225] Differential Scanning Calorimetry

[0226] Melting point(s) (in °C), heat of fusion (in J / g) and crystallinity (in %) were determined using differential scanning calorimetry (DSC) as follows: the instrument was first calibrated with indium; after the calibration, a polymer specimen is equilibrated at -50°C and then the temperature was increased to 200°C at a heating rate of 10°C / min; the melt was then kept isothermally at 200°C for five minutes; the melt was then cooled to -50°C at a cooling rate of 10°C / min and kept at -50°C for five minutes; the specimen was then heated to 200°C at a heating rate of 10°C / min. The DSC melting point(s), heat of fusion and crystallinity were reported from the second heating cycle. The primary melting point was reported according to the tallest peak melting temperature measured from the baseline. Heat of fusion was calculated by integrating the DSC thermogram from 20°C to the end of melting.

[0227] Film Dart Impact

[0228] Film dart impact strength was determined using ASTM DI 709-09 Method A (May 1, 2009). In this disclosure, the dart impact test employed a 1.5-inch (~ 38 mm) diameter hemispherical headed dart.

[0229] Film Tensile Properties

[0230] The following film tensile properties were determined using ASTM D882-12 (August 1, 2012): tensile break strength (MPa), elongation at break (%), tensile yieldstrength (MPa), tensile elongation at yield (%) and film toughness or total energy to break (ft·lb / in3). Tensile properties were measured in the both the machine direction (MD) and the transverse direction (TD) of the blown films.

[0231] Film Secant Modulus

[0232] The secant modulus is a measure of film stiffness. The secant modulus is the slope of a line drawn between two points on the stress-strain curve, i.e., the secant line. The first point on the stress-strain curve is the origin, i.e., the point that corresponds to the origin (the point of zero percent strain and zero stress), and; the second point on the stress-strain curve is the point that corresponds to a strain of 1%; given these two points the 1% secant modulus is calculated and is expressed in terms of force per unit area (MPa). The 2% secant modulus is calculated similarly. This method is used to calculated film modulus because the stress-strain relationship of polyethylene does not follow Hook’s law; i.e., the stress-strain behavior of polyethylene is non-linear due to its viscoelastic nature. Secant moduli were measured using a conventional Instron tensile tester equipped with a 200 Ibf load cell. Strips of monolayer film samples were cut for testing with following dimensions: 14 inch long, 1 inch wide and 1 mil thick; ensuring that there were no nicks or cuts on the edges of the samples. Film samples were cut in both the machine direction (MD) and the transverse direction (TD) and tested. ASTM conditions were used to condition the samples. The thickness of each film was accurately measured with a hand-held micrometer and entered along with the sample name into the Instron software. Samples were loaded in the Instron with a grip separation of 10 inch and pulled at a rate of 1 inch / min generating the strain-strain curve. The 1% and 2% secant modulus were calculated using the Instron software. Film Oxygen Transmission Rate and Water Vapor Transmission Rate

[0233] The water vapor transmission rate (WVTR) expressed in grams of water vapor transmitted per 100 square inches of film per day at a specified film thickness or g / 100 in2 / day was measured using a MOCON PERMATRAN-W® 3 / 33 manufactured by MOCON Inc, Minneapolis, Minnesota, USA. at conditions of 100°F (37.8°C) and 100% relative humidity. The WVTR test was run in duplicate and the average WVTR was reported.

[0234] The oxygen transmission rate (O2TR or OTR) expressed in cubic centimeters of oxygen per 100 square inches of film per day at a specified film thickness or cm3 / 100 in2 / day was measured using a MOCON OX- TRAN® 2 / 20 instrument manufactured by MOCON Inc, Minneapolis, Minnesota, USA. The film sample area used for testing was 100 cm2. The instrument has two test cells (A and B) and each film sample was analyzed in duplicate. The OTR result reported is the average of the results from these two test cells (Aand B). The test is carried out at a temperature of 23°C and at a relative humidity of 0%. The carrier gas used was 2% hydrogen gas in a balance of nitrogen gas and the test gas is ultra-high purity oxygen.

[0235] Film Optical Properties

[0236] Film optical properties were measured as follows: Haze, ASTM D1003-13 (November 15, 2013); and Gloss ASTM D2457- 13 (April 1, 2013).

[0237] Bimodal Polyethylene Blend A

[0238] Bimodal polyethylene blend A was an in-situ blend made using an unbridged phosphinimine single site catalyst in an in-series multi-reactor solution-phase polymerization process. The bimodal polyethylene blend A was made by forming a first ethylene polymer in a first reactor (Rl) in the presence of the single site catalyst and a forming a second ethylene polymer in a second reactor (R2) in the presence of the single site catalyst, wherein Rl and R2 were configured in series with one another. The first ethylene polymer and the second ethylene polymer were each an ethylene homopolymer. The Rl pressure was from about 14 MPa to about 18 MPa; while R2 was operated at a lower pressure to facilitate continuous flow from Rl to R2. Both Rl and R2 were continuously stirred reactors (CSTR’s) and were agitated to give conditions in which the reactor contents were well mixed. The process was operated continuously by feeding fresh process solvent, ethylene and hydrogen to the first and second reactors (Rl and R2) and in the removal of product. Methylpentane was used as the process solvent (a commercial blend of methylpentane isomers). Monomer (ethylene) was purified prior to addition to the reactor using conventional feed preparation systems — such as contact with various absorption media to remove impurities such as water, oxygen and polar contaminants.

[0239] In operating the continuous solution -phase polymerization process shown in Table 1, the total amount of ethylene supplied to the process was portioned or split between the two reactors Rl and R2. In Table 1, this operational variable was called the ethylene split (or ES), i.e., ESRland ESR2referred to the weight percent of ethylene injected in Rl and R2, respectively; with the proviso that ESR1+ ESR2= 100%.

[0240] In operating the continuous solution-phase polymerization process shown in Table 1, the total amount of ethylene converted in each reactor is monitored. The term QR1referred to the percent of the ethylene added to R1 that was polymerized by the single catalyst.

[0241] Similarly, QR2represented the percent of the ethylene added to R2 and residual ethylene flown into R2 that were polymerized by the single site catalyst, respectively.The following single site catalyst components were fed into each of the first reactor (Rl) and the second reactor (R2): component A, cyclopentadienyl tri(tertiarybutyl)phosphinimine titanium dichloride Cp[(t-Bu)3PN]TiCl2; component M, methylaluminoxane (MMAO-07); component B, trityl tetrakis(pentafluoro-phenyl)borate (trityl borate); and component P, 2,6-di-tert-butyl-4-ethylphenol (BHEB).

[0242] Methylaluminoxane (MMAO-07); and 2,6-di-tert-butyl-4-ethylphenol are premixed in-line and then combined with component A and component B just before entering the polymerization reactors (Rl and R2). The following catalyst component solvents were used: methylpentane for components M and P; and xylene for component A and B. The efficiency of the single site catalyst formulation was optimized by adjusting the quantity of component A added to Rl and R2 (Rl catalyst and R2 catalyst in ppm of Ti as recited in Table 1) and the mole ratios of the catalyst components — i.e., [M] / [A], [P] / [M] and [B] / [A] for each reactor.

[0243] Polymerization in the continuous solution-phase polymerization process was terminated by adding a catalyst deactivator to the second reactor exit stream. A passivator (DHT-4V CAS 11097-59-9) was added to the deactivated stream to form a passivated stream. A multi-stage phase separation process was employed to recover the bimodal polyethylene blend A from the process solvent in which the passivated stream was heated and passed through multiple V / L separators configured in series with one another. The polymer-rich stream exiting the last V / L separator, which contained greater than about 94 weight percent of the bimodal polyethylene blend A, was fed to a twin-screw extruder for addition of additives; namely: antioxidants AO 1076 (CAS 2082-79-3) and AO 168 (CAS 31570-04-4) at a combined target content of 1000 ppm based on the total weight of the bimodal polyethylene blend A; and nucleating agent HYPERFORM® HPN-20E at a target content of 1200 ppm based on the total weight of the bimodal polyethylene blend A). The nucleating agent HYPERFORM® HPN-20E was a combination of 34.0 wt.% zinc stearate and 66.0 wt.% calcium salt of 1,2-cyclohexanedicarboxylic acid. The twin screw extruder then directed the molten formulated bimodal polyethylene blend A* — i.e., the base or matrix bimodal polyethylene blend A, catalyst deactivator, passivator, antioxidants and the nucleating agent — to a pelletizer where the molten stream was extruded through a plurality of holes in a die plate of the pelletizer and into a water flushed cavity thereby leading to formation of strands. These strands were continuously cut into pellets by one or more rotating die plate cutters.With reference to Table 2, the formulated bimodal polyethylene blend A* had a number-average molecular weight, Mn, of 9,173 g / mol; a weight-average molecular weight, Mw, of 93,687 g / mol; a z-average molecular weight, Mz, of 296,639 g / mol; a Mw / Mnof 10.21; a Mz / Mw of 3.17; a Mz / Mn of 32.34; a density of 0.967 g / cm3; a melt index h of 1.2 dg / min; a stress exponent of 1.36; and a I21 / I2 of 55.

[0244] TABLE 1: Continuous Solution-Phase Polymerization Process Conditions: Bimodal Polyethylene Blend A,

[0245] Total Solution Rate, TSR (Mg / h) 378.9

[0246] R1 Total Solution Rate, TSRR1(Mg / h) 220.4

[0247] R2 Total Solution Rate, TSRR2(Mg / h) 373.5

[0248] Overall Ethylene Concentration (weight percent) 14.43

[0249] Ethylene Split, ESR1 / ESR2(weight percent) 45 / 55

[0250] Ethylene Concentration in Fresh Feed to R1 (weight percent) 11.01

[0251] Ethylene Concentration in Fresh Feed to R2 (weight percent) 18.68

[0252] H2R1(ppm) 1.28

[0253] H2R2(ppm) 30

[0254] R1 Inlet Temperature (°C) 21.5

[0255] R2 Inlet Temperature (°C) 18.7

[0256] R1 Mean Temperature (°C) 161

[0257] R2 Mean Temperature (°C) 192

[0258] R1 Ethylene Conversion, QR1(percent) 93.5

[0259] R2 Ethylene Conversion, QR2(percent) 84.4

[0260] R1 Catalyst, Single-Site Molecule (ppm Ti) 0.006344

[0261] R1 ([M] / [A]) Mole Ratio 144

[0262] R1 ([P] / [M]) Mole Ratio 0.30

[0263] R1 ([B] / [A]) Mole Ratio 1.17

[0264] R2 Catalyst, Single-Site Molecule (ppm Ti) 0.03

[0265] R2 ([M] / [A]) Mole Ratio 29

[0266] R2 ([P] / [M]) Mole Ratio 0.3

[0267] R2 ([B] / [A]) Mole Ratio 1.3

[0268] Polyethylene Production Rate (Mg / h) 49.94

[0269]

[0270] The Mw, Mn and weight percent of the first and second ethylene polymers were calculated and shown in Table 2 by inputting the actual reaction conditions into a reactor kinetics model. For references on relevant reactor kinetics modeling methods, see “Copolymerization” by A. Hamielec, J. MacGregor, and A. Penlidis in ComprehensivePolymer Science and Supplements, volume 3, Chapter 2, page 17, Elsevier, 1996 and “Copolymerization of Olefins in a Series of Continuous Stirred-Tank Slurry-Reactors using Heterogeneous Ziegler-Natta and Metallocene Catalysts. I. General Dynamic Mathematical Model” by J. B. P Soares and A. E Hamielec in Polymer Reaction Engineering, 4(2&3), p. 153, 1996.

[0271] The model took for input the flow of catalyst components (singe site catalyst molecule, alkylaluminoxane co-catalyst, the ionic activator and the hindered phenol), ethylene, hydrogen, and solvent provided to each reactor, the temperature (in each reactor), and the conversion of ethylene (in each reactor) and calculated the polymer properties made in each reaction zone using a terminal kinetic model for continuously stirred tank reactors (CSTRs) connected in series. The phrase “terminal kinetic model” assumes that the kinetics depend upon the monomer unit within the polymer chain on which the active catalyst site is located — e.g., see “Copolymerization” by A. Hamielec, J. MacGregor, and A. Penlidis in Comprehensive Polymer Science and Supplements, Volume 3, Chapter 2, page 17, Elsevier, 1996. In the model, the polymer chains were assumed to be of reasonably large molecular weight to ensure that the statistics of monomer unit insertion at the active catalyst center was valid and that monomers consumed in routes other than propagation were negligible. This is known as the “long chain” approximation.

[0272] The terminal kinetic model for polymerization included reaction rate equations for activation, initiation, propagation, chain transfer, and deactivation pathways. This model solved the steady-state conservation equations (e.g., the total mass balance and heat balance) for the reactive fluid which comprised the reactive species identified above.

[0273] In the model, the total mass balance for each CSTR was defined by eq. 1:

[0274]

[0275] i

[0276] (eq- 1)

[0277] where ṁi represents the mass flow rate of individual streams with index i indicating the inlet and outlet streams. Eq. 1 can be further expanded to show the individual species and reactions:

[0278] 0 = Σᵢ (ṁᵢxᵢⱼ / Mᵢ) / ρmixV + Rⱼ / ρmix

[0279] (eq- 2)where Mᵢ is the average molar weight of the fluid inlet or outlet i, xᵢⱼ is the mass fraction of species j in stream i, ρmix is the molar density of the reactor mixture, V is the reactor volume, Rⱼ is the reaction rate for species j, which has units of kmol / m3s.

[0280] In the model, the total heat balance was solved for an adiabatic reactor and was defined by:

[0281]

[0282] (eq- 3)

[0283] where, ṁᵢ is the mass flow rate of stream i (inlet or outlet), ΔHᵢ is the difference in enthalpy of stream i versus a reference state, qRx is the heat released by reaction(s), V is the reactor volume, Ẇ is the work input (i.e., agitator), Q̇ is the heat input / loss.

[0284] The single site catalyst molecule concentration input to each reactor was adjusted to match the experimentally determined ethylene conversion and reactor temperature values in order to solve the equations of the kinetic model (e.g., propagation rates, heat balance and mass balance). The H2 concentration input to each reactor may be likewise adjusted so that the calculated molecular weight distribution of a polymer made over all reactors (and, hence, the molecular weight of polymer made in each reactor) matches that which was observed experimentally.

[0285] Reported weight percent values shown in Table 2 are such that the sum of the weight percent of the material made in R1 and R2 (i.e., the first ethylene polymer and the second ethylene polymer) is at 100 percent.

[0286] In the model, the degree of polymerization, dpn, for a homopolymerization reaction was defined by the ratio of the rate of chain propagation reactions over the rate of chain transfer / termination reactions:

[0287] _ _ kpki] _ _ Rp

[0288]

[0289] 3“ + kf H [ff] Rt

[0290] (eq- 4)

[0291] where kPwas the propagation rate constant for adding monomer (ethylene) to a growing polymer chain, [m₁] is the molar concentration of monomer (ethylene) in the reactor, ktmwas the termination rate constant for chain transfer to ethylene, ktswas rate constant for the spontaneous chain termination, ktHwas the rate constant for the chain termination by hydrogen.

[0292] The number average molecular weight (Mn) for a polymer follows from the degree of polymerization and the molecular weight of a monomer unit. In the model, from thenumber average molecular weight of polymer in a given reactor, and assuming a Flory-Schulz distribution for a single site catalyst, the molecular weight distribution was determined for the polymer using the following relationships.

[0293] w(n) = nτ2e-τn

[0294] (eq- 5)

[0295] where n was the number of monomeric units in a polymer chain, w(n) was the weight fraction of polymer chains having a chain length n, and τ was calculated using the equation below:

[0296]

[0297] dpnRp

[0298] (eq- 6)

[0299] where dpn, Rp and Rt were the same as those defined in eq. The Flory-Schulz distribution can be transformed into the common log scaled gel permeation chromatography (GPC) trace by applying:

[0300] dW / d log₁₀(M) = ln(10) · n² / dpₙ² · e^(−n / dpₙ)

[0301]

[0302] dlog10(M) dpn

[0303] (eq- 7)

[0304] where the left-hand-side in eq. 7 is the differential weight fraction of polymer with a chain length n (n = M / 28 where 28 is the molecular weight of the polymer segment corresponding to a C2H4unit). From the Flory-Schulz distribution, the Mn, Mwand Mzof the polymer made in each reactor are: Mn, / = 28 * dpn,i, Mw, / = 2*Mn, / and Mz, / = 1.5 *MW, / for / = 1 or 2 where I = 1 corresponds to the first ethylene polymer made in the first reactor and I = 2 corresponds to the second ethylene polymer made in the second reactor.

[0305] The overall molecular weight distribution over both reactors — i.e., the overall molecular weight distribution of the bimodal polyethylene blend A — was modelled according to the sum of the molecular weight distribution of the polymer made in each reactor, and where each Flory-Schulz distribution was multiplied by the weight fraction of polymer each reactor:

[0306] 77— -7T7T = wR1ln(10)- -Pnl' +WR2 ln(10)- - 2ek Pn’2'

[0307]

[0308] id log10(M)Jorera(;dpn ldpn 2(eq- 8)

[0309] where the left-hand- si de in eq. 8 is the differential weight fraction of polymer with a chain length n, WRI and vi’iu on the right-hand-side are the weight fraction of the polymer made in each reactor, dpnRi and dpnR2 are the average degree of polymerization of the polymer madein each reactor — i.e., 28 dpn,1 = Mn,1 and 28×dpn,2 = Mn,2. The weight fraction of material made in each reactor was determined from knowing the mass flow of ethylene into each reactor along with knowing the conversion of ethylene in each reactor.

[0310] With reference to Table 2, the bimodal polyethylene blend A contained 45 weight percent of a first ethylene polymer having a number-average molecular weight Mn,i of 91,800 g / mol, a weight-average molecular weight Mw,i of 183,600 g / mol and a density pi of 0.9461 g / cm3. The bimodal polyethylene blend contained 55 weight percent of a second ethylene polymer having a number-average molecular weight Mn,2 of 6,200 g / mol, a weightaverage molecular weight Mw,2 of 12,400 g / mol and a density p2 of 0.9692 g / cm3.

[0311] Table 2 also includes the density of the first ethylene polymer and the second ethylene, i.e., ρ₁ and ρ₂, which were determined using the following equation:

[0312] 1 / ρₗ = 1.0142 + 0.0303 × [log₁₀(10⁻³ × Mₙ,ₗ)]^0.9804 / 1.3712

[0313] for / = 1 or 2

[0314] (eq- 9)

[0315] TABLE2: The Experimentally Measured Properties of the Formulated Bimodal Polyethylene Blend A* and the Properties of the First Ethylene Polymer and the Second Ethylene Polymer,

[0316] Formulated Bimodal Polyethylene Blend A* First Ethylene Polymer p (g / cm3) 0.967 wi (weight percent) 45*

[0317] I2 (dg / min) 1.2 Mn,i (g / mol) 91,800* Stress Exponent (-) 1.36 Mw,i (g / mol) 183,600* I21 / I2 (-) 55 ρ₁ (g / cm3) 0.9461†Mn (g / mol) 9,173 Second Ethylene Polymer Mw(g / mol) 93,687 W2 (weight percent) 55* Mz(g / mol) 296,639 Mn.2 (g / mol) 6,200* (Mw / Mn) (-) 10.21 MW,2 (g / mol) 12,400*

[0318]

[0319] P2 (g / cm3) 0.9692t

[0320] * Calculated by the reactor kinetic model described in eq. 1 to eq. 8; and

[0321] t Calculated by eq. 9.

[0322] Ethylene Polymer Products E** and F**

[0323] The formulated bimodal polyethylene blend A* was melt-blended with 1×104parts per million of third ethylene polymer B and third ethylene polymer C, respectively, to form ethylene polymer products E** and F**. Third ethylene polymer B was POLYWAX™ 2000, an ethylene homopolymer commercially available from NuCera Solutions. Third ethylene polymer C was POLYWAX™ 1000, an ethylene homopolymer commerciallyavailable from NuCera Solutions. The melt blending step was conducted by a Coperion ZSK 26 co-rotating twin screw extruder with an L / D of 32: 1 at a nitrogen purge flow rate of 4 liters per minute, a screw rotation speed of 200 rpm, an output rate of 20-22 kg / h, and a melt temperature of 222-224°C. The twin screw extruder was fitted with an underwater pelletizer and a Gala spin dryer. The materials were co-fed to the extruder using gravimetric feeders to achieve the desired loading of the third ethylene polymer.

[0324] Basic properties — molecular weight distribution characteristics as determined by the conventional GPC method described in the Testing Methods section and second melting interval attributes as determined by the DSC method described in the Testing Methods section — of the third ethylene polymer B and third ethylene polymer C are shown in Table 3. In Table 3, the weight percent of material having a molecular weight (MW) greater than 1,000 g / mol (1 kg / mol) and less than 10,000 g / mol (10 kg / mol) was calculated by summing the weight fraction of GPC fractions which had a molecular weight (MW) of greater than 1,000 g / mol and less than 10,000 g / mol in the conventional GPC experiment at a ∆(log10MW) ≈ 0.003. With reference to Table 3, third ethylene polymer B had a numberaverage molecular weight, Mn, of 2,340 g / mol; a weight-average molecular weight, Mw, of 2,610 g / mol; a z-average molecular weight, Mz, of 2,870 g / mol; a Mw / Mnof 1.12; a primary melting temperature of 123.1°C; a secondary melting temperature of 98.8°C; a heat of fusion of 270.0 J / g; a crystallinity of 93.1%; and 98.9 wt.% of material having a MW of greater than 1,000 g / mol and less than 10,000 g / mol.

[0325] TABLE 3: Molecular Weight Distribution Characteristics and Second Melting Interval Attributions of the Third Ethylene Polymers B and C.

[0326] Third Ethylene Third Ethylene Polymer B Polymer C Mn (g / mol) 2,340 1,290

[0327] Mw(g / mol) 2,610 1,420

[0328] Mz(g / mol) 2,870 1,550 Mw / Mn (-) 1.12 1.10 Weight percent of material having 1,000 98.9 87.2 g / mol < MW < 10,000 g / mol (wt.%)

[0329] Primary Tm(°C) 123.1 111.6 Secondary Tm (°C) 98.8 69.1 Heat of Fusion, AHm(J / g) 270.0 250.6

[0330]

[0331] Crystallinity (%) 93.1 86.4With reference to Table 3, third ethylene polymer C had a number-average molecular weight, Mn, of 1,290 g / mol; a weight-average molecular weight, Mw, of 1,420 g / mol; a z-average molecular weight, Mz, of 1,550 g / mol; a Mw / Mnof 1.10; a primary melting temperature of 111.6°C; a secondary melting temperature of 69.1°C; a heat of fusion of 250.6 J / g; a crystallinity of 86.4%; and 87.2 wt.% of material having a MW of greater than 1,000 g / mol and less than 10,000 g / mol.

[0332] Ethylene Polymer Products G**

[0333] The formulated bimodal polyethylene blend A* was melt-blended with 1×104parts per million of third ethylene polymer D. Third ethylene polymer D was POLYWAX™ 3000, an ethylene homopolymer commercially available from NuCera Solutions. The melt blending step was conducted by a Coperion ZSK 26 co-rotating twin screw extruder with an L / D of 32: 1 at a nitrogen purge flow rate of 4 liters per minute, an output rate of 20 kg / h, and a melt temperature of 222-224°C. The twin screw extruder was fitted with an underwater pelletizer and a Gala spin dryer. The materials were co-fed to the extruder using gravimetric feeders to achieve the desired loading of the third ethylene polymer.

[0334] Basic properties — molecular weight distribution characteristics as determined by the conventional GPC method described in the Testing Methods section and second melting interval attributions as determined by the DSC method described in the Testing Methods section — of the third ethylene polymer D are shown in Table 4. In Table 4, the weight percent of material having a molecular weight (MW) greater than 1,000 g / mol and less than 10,000 g / mol was calculated by summing the weight fraction of GPC fractions which had a molecular weight (MW) of greater than 1,000 g / mol and less than 10,000 g / mol in the conventional GPC experiment at a ∆(log10MW) ≈ 0.003.

[0335] With reference to Table 4, third ethylene polymer D had a number-average molecular weight, Mn, of 3,210 g / mol; a weight-average molecular weight, Mw, of 3,790 g / mol; a z-average molecular weight, Mz, of 4,300 g / mol; a Mw / Mnof 1.18; a primary melting temperature of 129.16°C (no secondary melting temperature was observed); a heat of fusion of 230.4 J / g; a crystallinity of 80.8%; and 98.6 wt.% of material having a MW of greater than 1,000 g / mol and less than 10,000 g / mol.TABLE 4: Molecular Weight Distribution Characteristics and Second Melting Interval Attributes of the Third Ethylene Polymer D,

[0336] Third Ethylene Polymer D Mn (g / mol) 3,210

[0337] Mw(g / mol) 3,790

[0338] Mz(g / mol) 4,300

[0339] Mw / Mn (-) 1.18

[0340] Weight percent of material having 1,000 g / mol 98.6

[0341] < MW < 10,000 g / mol (wt.%)

[0342] Primary Tm(°C) 129.16

[0343] Secondary Tm (°C) Not observed

[0344] Heat of Fusion, AHm(J / g) 230.4

[0345]

[0346] Crystallinity (%) 80.8

[0347] Ethylene Polymer Products K**, L** and M**

[0348] The formulated bimodal polyethylene blend A* was melt-blended with 0.5×104, 1×104and 2×104parts per million of third ethylene polymer J to form ethylene polymer products K**, L** and M**. Third ethylene polymer J was LICOCENE® PE 5301, an ethylene homopolymer commercially available from Clariant International Ltd. The melt blending step was conducted by a Coperion ZSK 26 co-rotating twin screw extruder with an L / D of 32: 1 at a nitrogen purge flow rate of 4 liters per minute, an output rate of 20 kg / h, and a melt temperature of 222-224°C. The twin screw extruder was fitted with an underwater pelletizer and a Gala spin dryer. The materials were co-fed to the extruder using gravimetric feeders to achieve the desired loading of the third ethylene polymer. Basic properties — molecular weight distribution characteristics as determined by the conventional GPC method described in the Testing Methods section and second melting interval attributions as determined by the DSC method described in the Testing Methods section — of the third ethylene polymer D are shown in Table 5. In Table 5, the weight percent of material having a molecular weight (MW) greater than 1,000 g / mol and less than 10,000 g / mol was calculated by summing the weight fraction of GPC fractions which had a molecular weight (MW) of greater than 1,000 g / mol and less than 10,000 g / mol in the conventional GPC experiment at a ∆(log10MW) ≈ 0.003.

[0349] With reference to Table 5, third ethylene polymer D had a number-average molecular weight, Mn, of 2,336 g / mol; a weight-average molecular weight, Mw, of 5,704 g / mol; a z-average molecular weight, Mz, of 14,075 g / mol; a Mw / Mnof 2.44; a primarymelting temperature of 121.1°C; a heat of fusion of 276.8 J / g; a crystallinity of 95.5%; and 78.0 wt.% of material having a MW of greater than 1,000 g / mol and less than 10,000 g / mol.

[0350] TABLE 5: Molecular Weight Distribution Characteristics and Second Melting Interval Attributes of the Third Ethylene Polymer J,

[0351] Third Ethylene Polymer J Mn (g / mol) 2,336

[0352] Mw(g / mol) 5,704

[0353] Mz(g / mol) 14,075

[0354] Mw / Mn (-) 2.44

[0355] Weight percent of material having 1,000 g / mol 78.0

[0356] < MW < 10,000 g / mol (wt.%)

[0357] Primary Tm(°C) 121.1

[0358] Secondary Tm (°C) Not observed

[0359] Heat of Fusion, AHm(J / g) 276.8

[0360]

[0361] Crystallinity (%) 95.5

[0362] Monolayer Blown Films

[0363] Monolayer blown films were generated using a 2.5-inch Gloucester blown film line (L / D = 24) equipped with a barrier screw, a low pressure 4-inch (10.16 cm) diameter die and a Western Polymer Air ring. The extruder was equipped with the following screen pack: 20 / 40 / 60 / 80 / 20 mesh. The monolayer blown films were produced at a thickness of about 1.5 mil (38.1 pm); at a blow-up ratio (BUR) of 2.0; at a die gap of 35 mils (0.0889 cm); by maintaining a constant output rate of 100 Ib / hr (45.4 kg / hr) by adjusting extruder screw speed; and by maintaining a frost line height of 15-18 inch (38.1-45.72 cm) by adjusting the cooling air. To avoid melt fracture, 0-3 weight percent of a process aid masterbatch which was a 5-weight percent masterbatch of 3M™ DYNAMAR™ FX 5920A in an LLDPE carrier resin was dry blended with the test product prior to the extrusion step.

[0364] Comparative monolayer blown films CFA*1, CFA*2 and CFA*3 were prepared from the formulated bimodal polyethylene blend A* and 0, 1.5 and 3 weight percent of the process aid masterbatch, respectively.

[0365] Comparative monolayer blown films CFK1 and CFK2 were prepared from two different lot numbers of SURPASS® HPs267-AB, a high-density polyethylene commercially available from NOVA Chemicals Corporation. SURPASS® HPs267-AB has a nominal density of 0.967 g / cm3and a nominal melt index I2 of 2.0 dg / min. Comparative monolayer blown films CFK1 and CFK2 contained 3 weight percent of the process aid masterbatch.Comparative monolayer blown films CFL1 and CFL2 were prepared from two different lot numbers of SURPASS® HPx267-AB, a high-density polyethylene commercially available from NOVA Chemicals Corporation. SURPASS® HPx267-AB has a nominal density of 0.967 g / cm3and a nominal melt index I2of 2.0 dg / min. Comparative monolayer blown films CFL1 and CFL2 contained 3 weight percent of the process aid masterbatch.

[0366] Comparative monolayer blown films CFM1, CFM2 and CFM3 were prepared from a dry blend of the formulated bimodal polyethylene blend A* and, respectively, 1% (by weight) of a 5%-masterbatch of talc powder (POLYBLOC® CAS registry 14807-96-6), 1% (by weight) of a 15%-masterbatch of talc powder (POLYBLOC® CAS registry 14807-96-6) and 3% (by weight) of a 15%-masterbatch of talc powder (POLYBLOC® CAS registry 14807-96-6). The carrier resin for the talc masterbatches was a 2 g / 10 min melt index, 0.920 g / cm3density 1 -butene LLDPE. The formulated bimodal polyethylene blend A* and the talc masterbatches were dry blended prior to the extrusion step using a WSB-241-T MAGUIRE blender. Comparative monolayer blown films CFM1, CFM2 and CFM3 contained 500, 1500 and 4500 parts per million of talc, respectively. These comparative blown films contained 1.5 weight percent of the process aid masterbatch.

[0367] Monolayer blown films FE** and FF** were prepared from the ethylene polymer products E** and F** respectively. These blown films contained 1.5 weight percent of the process aid masterbatch.

[0368] Monolayer blown films FG***, FH*** and FI*** were prepared from the ethylene polymer product G** and, respectively, 1.3%, 2.7%, and 4% (by weight) of a 15% talc powder masterbatch (pre-dispersed in a 2 g / 10 min melt index, 0.920 g / cm3density 1-butene LLDPE carrier resin). These blown films respectively contained 1,950, 4,050, and 6,000 parts per million of talc powder. Talc powder was POLYBLOC® talc (CAS registry 14807-96-6), a mineral anti-blocking additive commercially available from Mineral Technologies. These blown films contained 1.5 weight percent of the process aid masterbatch.

[0369] Monolayer blown films FK**, FL** and FM** were prepared from the ethylene polymer products K**, L** and M**, respectively. These blown films contained 1.5 weight percent of the process aid masterbatch.

[0370] Tables 6A-6D compares the barrier, mechanical and optical properties of the monolayer blown films described herein above in this section.TABLE 6A: Monolayer Blown Films Barrier, Optical and Mechanical Properties.

[0371] Unit CFA*1 CFA*2 CFA*3 CFK1 CFK2 Base Resin — Form ulated Bimodal SURPASS® Polyet rylene Blend A* HPs267-AB Third Ethylene Polymer Type (ppm) — — — — — Mineral Anti-Blocking Type (ppm) — — — — — Additive

[0372] OTR cm3 / 100in2 / day 31.46 28.44 27.68 32.25 27.47 nOTR:cm3 / 100in2 / day 31.46 32.23 27.68 30.10 27.47 WVTR g / 100 in2 / day 0.0910 0.0814 0.0802 0.0837 0.0755 nWVTR:g / 100 in2 / day 0.0910 0.0923 0.0802 0.0781 0.0755 Gloss 45° 0 / / o 29.95 22.63 23.57 22.51 23.32 Haze 0 / / o 30.34 35.80 33.18 36.67 33.83 Dart Impact g / mil < 21.4 < 20.0 < 20.0 17.3 <20.0 MD Yield Stress MPa 31.6 30.2 30.2 31.2 35.6 MD Stress at Break MPa 38.1 40.6 40.6 37.7 39.5 MD Tensile Energy J 11.22 10.82 10.82 11.9 10.93 MD 1% Secant Modulus MPa 1011 743 743 1080 1255 MD 2% Secant Modulus MPa 897 737 737 881 1005 MD Toughness ft.lb / in32652.4 2599.4 2599.4 2827.2 3017.3 MD Elongation at Yield 0 / / o 9 9 9 8 9 MD Elongation at Break 0 / / o 842 825 825 949 904 TD Yield Stress MPa 35.3 34.5 34.5 34.9 39.7 TD Stress at Break MPa 35.3 34.5 34.5 34.9 39.7 TD Tensile Energy J 0.08 0.06 0.06 0.06 0.07 TD 1% Secant Modulus MPa 1500 816 816 1041 1449 TD 2% Secant Modulus MPa 1228 897 897 1055 1308 TD Toughness ft.lb / in318.6 13.8 13.8 13.9 18 TD Elongation at Yield 0 / / o 6 5 5 5 5

[0373]

[0374] TD Elongation at Break 0 / / o 6 5 5 5 6 t Normalized transmission rates (TRs) were calculated according to: nTR = (actual TR) x (actual thickness in mil) / (target thickness in mil) where the actual TR is the experimentally measured transmission rate (in cm3 / 100in2 / day for OTR or in g / 100 in2 / day for WVTR). Target thickness was 1.5 mils, and the actual thickness was the average of three thickness measurements in mils, using a micrometer.

[0375] TABLE 6B: Monolayer Blown Films Barrier, Optical and Mechanical Properties.

[0376] Unit CFL1 CFL2 CFM1 CFM2 CFM3 Base Resin — SURPASS® Form ulated Bimodal HPx267-AB Polyet rylene Blend A* Third Ethylene Polymer Type (ppm) — — — — — Mineral Anti-Blocking Type (ppm) — — Talc Talc Talc Additive (500) (1500) (4500) OTR cm3 / 100in2 / day 22.16 24.79 32.69 33.27 34.72 nOTR:cm3 / 100in2 / day 22.16 23.14 32.69 33.27 34.72 WVTR g / 100 in2 / day 0.0713 0.0674 0.0929 0.0958 0.1018 nWVTR:g / 100 in2 / day 0.0713 0.0629 0.0929 0.0958 0.1086

[0377] 0 /

[0378]

[0379] Gloss 45° / o 35.78 29.18 21.47 20.4 17.28Haze 0 / / o 25.08 27.37 35.38 38.07 42.05 Dart Impact g / mil < 20.0 < 20.0 18.5 17.3 17.3 MD Yield Stress MPa 31.4 36.2 29.6 30.4 29.4 MD Stress at Break MPa 37.3 39.4 37.4 33.2 36.7 MD Tensile Energy J 12.27 10.23 9.7 8.2 9.3 MD 1% Secant Modulus MPa 1152 1321 854 946 792 MD 2% Secant Modulus MPa 905 1027 753 804 752 MD Toughness ft.lb / in32898.9 2902.8 2310.6 1953.3 2178.5 MD Elongation at Yield 0 / / o 8 9 10 10 10 MD Elongation at Break 0 / / o 987 877 768 671 737 TD Yield Stress MPa 35 40.6 34 34.3 34.3 TD Stress at Break MPa 34.9 40.6 34 34.3 34.3 TD Tensile Energy J 0.07 0.06 0.06 0.06 0.07 TD 1% Secant Modulus MPa 1568 1708 1090 828 1430 TD 2% Secant Modulus MPa 1241 1380 1049 901 1129 TD Toughness ft.lb / in315.8 18.1 14.8 13.4 16.2 TD Elongation at Yield 0 / / o 5 5 6 5 6

[0380]

[0381] TD Elongation at Break 0 / / o 5 5 6 5 6 t Normalized transmission rates (TRs) were calculated according to: nTR = (actual TR) x (actual thickness in mil) / (target thickness in mil) where the actual TR is the experimentally measured transmission rate (in cm3 / 100in2 / day for OTR or in g / 100 in2 / day for WVTR). Target thickness was 1.5 mils, and the actual thickness was the average of three thickness measurements in mils, using a micrometer.

[0382] TABLE 6C: Monolayer Blown Films Barrier, Optical and Mechanical Properties.

[0383] Unit FE** FF** FG*** FH*** FI*** Base Resin — Formulated Bimodal Polyethylene Blend A* Third Ethylene Polymer Type (ppm) B C D D D (IxlO4) (IxlO4) (IxlO4) (IxlO4) (IxlO4) Mineral Anti-Blocking Type (ppm) — — 1950 4050 6000 Additive

[0384] OTR cm3 / 100in2 / day 24.98 25.47 26.05 28.46 28.46 nOTR:cm3 / 100in2 / day 21.65 23.77 26.05 26.56 28.46 WVTR g / 100 in2 / day 0.0717 0.0727 0.0777 0.0845 0.0862 nWVTR:g / 100 in2 / day 0.0621 0.0679 0.0777 0.0789 0.0862 Gloss 45° 0 / / o 30.16 30.33 23.39 24.27 21.91 Haze 0 / / o 28.47 26.68 32.87 34.43 36.46 Dart Impact g / mil < 20 < 20 < 20 < 20 < 20 MD Yield Stress MPa 35 36 33.2 34.1 33.6 MD Stress at Break MPa 40 40.1 36 35.7 37.2 MD Tensile Energy J 10.03 10.35 9.41 9.3 9.27 MD 1% Secant Modulus MPa 1188 1181 1200 1190 1168 MD 2% Secant Modulus MPa 951 969 930 954 924 MD Toughness ft.lb / in32628.5 2750.4 2382.2 2399.1 2489 MD Elongation at Yield 0 / / o 10 9 9 9 9 MD Elongation at Break 0 / / o 787 806 769 769 784 TD Yield Stress MPa 43.1 43 40.4 40.7 40.4

[0385]

[0386] TD Stress at Break MPa 43.1 42.2 40.6 40.7 40.4TD Tensile Energy J 0.07 0.07 0.07 0.07 0.07 TD 1% Secant Modulus MPa 1717 1659 1722 1686 1572 TD 2% Secant Modulus MPa 1468 1473 1396 1363 1342 TD Toughness ft.lb / in318.8 18.6 18.3 18.7 17.9 TD Elongation at Yield 0 / / o 5 5 5 6 5

[0387]

[0388] TD Elongation at Break 0 / / o 5 5 5 6 5 ' Normalized transmission rates (TRs) were calculated according to: nTR = (actual TR) x (actual thickness in mil) / (target thickness in mil) where the actual TR is the experimentally measured transmission rate (in cm3 / 100in2 / day for OTR or in g / 100 in2 / day for WVTR). Target thickness was 1.5 mils, and the actual thickness was the average of three thickness measurements in mils, using a micrometer.

[0389] TABLE 6D: Monolayer Blown Films Barrier, Optical and Mechanical Properties.

[0390] Unit FK** FL** FM** Base Resin — Formulated Bimodal Polyethylene Blend A*

[0391] Third Ethylene Polymer Type (ppm) J (0.5xl04) J (lxl04) J (2xl04) Mineral Anti-Blocking Additive Type (ppm) — — — OTR cm3 / 100in2 / day 26.4 27.3 23 nOTR:cm3 / 100in2 / day 28.16 27.30 24.53 WVTR g / 100 in2 / day 0.0643 0.0663 0.0665 nWVTR:g / 100 in2 / day 0.0686 0.0663 0.0709 Gloss 45° 0 / / o 26.4 30.3 27 Haze 0 / / o 27.9 29.6 27.2 Dart Impact g / mil < 30 < 30 < 30 MD Yield Stress MPa 30.5 30.2 31.4 MD Stress at Break MPa 43.1 43.8 42.4 MD Tensile Energy J 11.86 11.84 11.18 MD 1% Secant Modulus MPa 1070 1025 1154 MD 2% Secant Modulus MPa 733 693 771 MD Toughness ft.lb / in32864.1 2931.3 2828.3 MD Elongation at Yield 0 / / o 9 9 9 MD Elongation at Break 0 / / o 898 917 879 TD Yield Stress MPa 37.9 38.2 39.3 TD Stress at Break MPa 33.9 37.8 39.3 TD Tensile Energy J 0.07 0.07 0.07 TD 1% Secant Modulus MPa 1899 1890 1857 TD 2% Secant Modulus MPa 1466 1464 1432 TD Toughness ft.lb / in317.3 16.8 17.8 TD Elongation at Yield 0 / / o 4 5 5

[0392]

[0393] TD Elongation at Break 0 / / o 5 5 5 ' Normalized transmission rates (TRs) were calculated according to: nTR = (actual TR) x (actual thickness in mil) / (target thickness in mil) where the actual TR is the experimentally measured transmission rate (in cm3 / 100in2 / day for OTR or in g / 100 in2 / day for WVTR). Target thickness was 1.5 mils, and the actual thickness was the average of three thickness measurements in mils, using a micrometer.With reference to Tables 6A-6D, the monolayer blown films FE**, FF**, FK**, FL** and FM** had a superior or comparable balance of barrier, optical and mechanical properties relative to those observed in the case of comparative monolayer blown films.

[0394] Tables 7A-7B highlight the relative difference between the barrier properties of the monolayer blown films FE**, FF**, FK**, FL** and FM** when compared to the comparative monolayer blown films CFA*l-3, CFK1-2 and CFL 1-2. Tables 7C-D summarize the relative difference between the monolayer blown films FG***, FH*** and FI*** relative to the comparative monolayer blown films CFA*l-3 and CFM1-3.

[0395] TABLE 7A: Relative Difference (A) Between the nOTR of the Monolayer Blown Films FE**, FF**, FK**, FL** and FM**, and the Comparative Monolayer Blown Films CFA*l-3, CFK1-2 and CFL 1-2,

[0396] At(%) FE** FF** FK** FL** FM** CFA*1 -31.2 -24.4 -10.5 -13.2 -22.0 CFA*2 -32.8 -26.2 -12.6 -15.3 -23.9 CFA*3 -21.8 -14.1 1.7 -1.4 -11.4 CFK1 -28.1 -21.0 -6.4 -9.3 -18.5 CFK2 -21.2 -13.5 2.5 -0.6 -10.7 CFL1 -2.3 7.3 27.1 23.2 10.7 CFL2 -6.4 2.7 21.7 18.0 6.0

[0397]

[0398] 'The relative difference (A) between the nOTRs were calculated according to: A = 100 x (nOTRex- nOTRcolnp) / nOTRcolnpwhere nOTRexwas the normalized OTR of the monolayer blown film FE**, FF**, FK**, FL** or FM**, and nOTRcolnpwas the normalized OTR of the monolayer blown films CFA*l-3 or CFK1-2 or CFL 1-2.

[0399] TABLE 7B: Relative Difference (A) Between the nWVTR of the Monolayer Blown Films FE**, FF**, FK**, FL** and FM**, and the Comparative Monolayer Blown Films CFA*l-3, CFK1-2 and CFL 1-2,

[0400] At(%) FE** FF** FK** FL** FM** CFA*1 -31.8 -25.4 -24.6 -27.1 -22.1 CFA*2 -32.7 -26.4 -25.7 -28.2 -23.2 CFA*3 -22.6 -15.3 -14.5 -17.3 -11.6 CFK1 -20.5 -13.1 -12.2 -15.1 -9.2 CFK2 -17.7 -10.1 -9.1 -12.2 -6.1 CFL1 -12.9 -4.8 -3.8 -7.0 -0.6 CFL2 -1.3 7.9 9.1 5.4 12.7

[0401]

[0402] 'The relative difference (A) between the nWVTRs were calculated according to: A = 100 x (nWVTRex-nWVTRcolnp) / nWVTRcolnpwhere nWVTRexwas the normalized WVTR of the monolayer blown film FE**, FF**, FK**, FL** or FM**, and nWVTRcolnpwas the normalized WVTTR of the monolayer blown films CFA*l-3 or CFK1-2 or CFL 1-2.With reference to Tables 7A-7B, the monolayer blown films FE**, FF**, FK**, FL** and FM** had an improved (i.e., A < 0) or comparable barrier properties for nOTR, nWVTR, or both, relative to those observed in the case of films prepared from the commercial resins SURPASS® HPs267-AB and SURPASS® HPx267-AB having a nominal melt index 2.0 dg / min — i.e., comparative monolayer blown films CFK1-2 and CFL 1-2. Those of ordinary skill in the art will appreciate that this observation is unexpected as a lower viscosity polymer matrix permitting faster relaxation processes in the melt state is expected to allow formation of more randomly orientated crystalline regions in the final film which enhances the tortuous path for the water or oxygen molecules, thus improving the barrier properties.

[0403] Additional comparative monolayer blown films CFA*4 and CFA*RC were respectively prepared from the formulated bimodal polyethylene blend A* and recompounded formulated bimodal polyethylene blend A*RC using the film blowing conditions disclosed herein above. The re-compounded formulated bimodal polyethylene blend A*RC was a “re-compounded” sample prepared by feeding the formulated bimodal polyethylene blend A* to a Coperion ZSK 26 co-rotating twin screw extruder with an L / D of 32: 1 at a nitrogen purge flow rate of 4 liters per minute, an output rate of 20-22 kg / h, and a melt temperature of 222-224°C. The comparative monolayer blown films CFA*4 and CFA*RC each contained 2 weight percent of the process aid masterbatch. The relative difference between the nOTR and nWVTR of the comparative monolayer blown films CFA*4 and CFA*RC were -14.9% and -14.5%, respectively. While not wishing to be limited by any single theory, the enhanced barrier properties of the comparative monolayer blown film CFA*RC, compared to CFA*4, can be attributed to the improved dispersion state of the nucleating agent achieved during the re-compounding stage. The monolayer blown films FE** and FF** exhibited a relative nOTR difference of -32.8% and -26.2%, and a relative nWVTR difference of -32.7% and -26.4%, respectively, compared to the comparative monolayer blown film CFA*2. The monolayer blown films FE** and FF**, and the comparative monolayer blown film CFA*2 each contained 1.5 weight percent of the process aid masterbatch.TABLE 7C: Relative Difference (A) Between the nOTR of the Monolayer Blown Films FG***, FH*** and FI*** Relative to the Comparative Monolayer Blown Films CFA*l-3 and CFM1-3,

[0404] At(%) FG*** FH*** FI***

[0405] CFA*1 -17.20 -15.58 -9.54

[0406] CFA*2 -19.17 -17.59 -11.70

[0407] CFA*3 -5.89 -4.05 2.82

[0408] CFM1 -20.31 -18.75 -12.94

[0409] CFM2 -21.70 -20.17 -14.46

[0410] CFM3 -24.97 -23.50 -18.03

[0411]

[0412] 'The relative difference (A) between the nOTRs were calculated according to: A = 100 x (nOTRex- nOTRcolnp) / nOTRcolnpwhere nOTRexwas the normalized OTR of the monolayer blown film FG*** or FH*** or FI***, and nOTRcolnpwas the normalized OTR of the monolayer blown films CFM1-3 or CFA*l-3.

[0413] TABLE 7D: Relative Difference (A) Between the nWVTR of the Monolayer Blown Films FG***, FH*** and FI*** Relative to the Comparative Monolayer Blown Films CFA*l-3 and CFM1-3,

[0414] At(%) FG*** FH*** FI***

[0415] CFA*1 -14.62 -13.30 -5.27

[0416] CFA*2 -15.82 -14.52 -6.61

[0417] CFA*3 -3.12 -1.62 7.48

[0418] CFM1 -16.36 -15.07 -7.21

[0419] CFM2 -18.89 -17.64 -10.02

[0420] CFM3 -28.45 -27.35 -20.63

[0421]

[0422] 'The relative difference (A) between the nWVTRs were calculated according to: A = 100 x (nWVTRex-nWVTRcolnp) / nWVTRcolnpwhere nWVTRexwas the normalized WVTR of the monolayer blown film FG*** or FH*** or FI***, and nWVTRcolnpwas the normalized WVTTR of the monolayer blown films CFM1-3 or CFA*l-3.

[0423] Further and importantly, with reference to Tables 7C-7D, it was observable that the monolayer blown films FG***, FH*** and FI*** had significantly improved barrier properties relative to the monolayer blown films CFM1-3 (note that comparative films CFM1-3 contained a smaller loading of talc). The monolayer blown films FG***, FH*** and FI*** had improved or comparable barrier properties as those observed in the case of films prepared from the bimodal polyethylene blend A* (i.e., films CFA*l-3).

[0424] Dusting characteristic of the monolayer blown films were examined as follows: (1) fixing a dark colored Velcro hoop tape as test swatch on a stationery mount; (2) drawing a fixed quantity of the test film sample across the test swatch under constant tension conditions for a fixed period of time; (3) observing the amount of the abraded material(dust) which is deposited on the test swatch; and (4) quantifying the area of coverage of dust on the test swatch by image analysis.

[0425] The test swatch was mounted on the blown film line (as described below) and the dusting test was completed as the monolayer film was being produced. The blown film line was equipped with a number of guide rolls which are located upstream of the film winder. These guide rolls direct the movement of the film as it is being pulled by the winding mechanism. The finished roll of film was produced on a shaft / roll which is driven by the film winder. The test swatch was taped to a guide roll that had been locked — i.e., the guide roll was not permitted to rotate. Thus, the plastic film was subjected to a frictional force as it was ragged across the fixed test swatch.

[0426] The film line was run for 60 minutes (at an essentially constant throughput rate and using an essentially constant tension load — as applied by the film winder). This procedure was repeated for all of the films. The black felt test swatch was removed at the end of each 60-minute test. A quantitative result was then obtained by photographing a section of the test swatch with a digital camera. The resulting digital image was then analyzed to measure the percentage of the surface which was white (indicating dusting area) and the percentage which remained black.

[0427] Table 8 compares the “dusting area” results for the monolayer blown films described herein above in this section. The monolayer blown films FG***, FH*** and FI*** had advantageously very low dusting area relative to the other tested film samples. To be specific, unlike the comparative films CFM1-3, films FG***, FH*** and FI*** exhibited low dusting propensity without compromising their barrier properties. To be specific, for example, the comparative monolayer blown film CFM3 contained 4500 ppm of talc and had a dusting area of 8.0%, a nOTR of 34.72 cm3 / 100 in2 / day and a nWVTR of 0.1086 g / 100 in2 / day. The monolayer blown film FH*** despite having a lower content of talc (4050 ppm) exhibited a dusting area of 3.0%, a nOTR of 26.56 cm3 / 100 in2 / day and a nWVTR of 0.0789 g / 100 in2 / day. It is also noticeable that the monolayer blown film FH*** despite its lower talc content (4050 ppm vs. 4500 ppm) had a significantly improved (lower) dusting area compared to the comparative monolayer blown film CFM3 (3.0% vs. 8.0%). The combination of improved dusting and barrier properties were also observed for the monolayer blown film FI*** (1.0% dusting area, 28.46 nOTR, 0.0862 nWVTR and contained 6000 ppm talc) when compared to the monolayer blown film CFM3 (8.0% dusting area, 34.72 nOTR, 0.1086 nWVTR and contained 4500 ppm talc).TABLE 8: “Dusting Area” Results for the Monolayer Blown Films.

[0428] Dusting Area nOTR nWVTR Talc Loading (%) (PPm) FE** 32.0 21.65 0.0621

[0429] FF** 32.0 23.77 0.0679 — FG*** 4.0 26.05 0.0777 1950 FH*** 3.0 26.56 0.0789 4050 FI*** 1.0 28.46 0.0862 6000 CFA*1 — 31.46 0.091 — CFA*2 28.0 32.23 0.0923 — CFA*3 27.0 27.68 0.0802 —

[0430] CFK1 29.0 30.1 0.0781 —

[0431] CFK2 44.0 27.47 0.0755 —

[0432] CFL1 25.0 22.16 0.0713 —

[0433] CFL2 38.0 23.14 0.0629 —

[0434] CFM1 22.0 32.69 0.0929 500 CFM2 15.0 33.27 0.0958 1500

[0435]

[0436] CFM3 8.0 34.72 0.1086 4500

[0437] EMBODIMENTS

[0438] Embodiment I. An ethylene polymer product, comprising: A) a bimodal polyethylene blend, the bimodal polyethylene blend comprising: a first ethylene polymer having a first weight-average molecular weight, Mw,1, of from about 50 kg / mol to about 250 kg / mol, a first poly dispersity index, Mq / Mn, of from about 1.7 to about 2.5, and a first density ρ1 of greater than about 0.94 g / cm3; and a second ethylene polymer having a second weight-average molecular weight, Mw,2, of from about 8 kg / mol to about 30 kg / mol, a second poly dispersity index, Mw,2 / Mn, of from about 1.7 to about 2.5, and a second density pi of greater than about 0.95 g / cm3; and B) from about 1×102parts per million to about 1×105parts per million of a third ethylene polymer, based on the total weight of the bimodal polyethylene blend; wherein the third ethylene polymer has a melting point of greater than 80°C, as determined by differential scanning calorimetry; and wherein the third ethylene polymer has a third weight-average molecular weight, v,3, satisfying the inequality M,3<- / W,2.

[0439] Embodiment II. The ethylene polymer product of embodiment I, wherein the ethylene polymer product further comprises C) from about 1 x 102parts per million to about 3 x 103parts per million of a nucleating agent, based on the total weight of the bimodal polyethylene blend.

[0440] Embodiment III. The ethylene polymer product of embodiment II, wherein the nucleating agent comprises a calcium salt of 1,2-cyclohexanedicarboxylic acid.Embodiment IV. The ethylene polymer product of any one of embodiments I to III, wherein the ethylene polymer product further comprises D) from about 5×102parts per million to about 104parts per million of an inorganic anti -blocking additive, based on the total weight of the bimodal polyethylene blend.

[0441] Embodiment V. The ethylene polymer product of embodiment IV, wherein the inorganic anti-blocking additive comprises talc.

[0442] Embodiment VI. The ethylene polymer product of any one of embodiments I to V, wherein the bimodal polyethylene blend is further characterized by at least one of the following features: (a) a polydispersity index, Mw / Mn, of from about 4 to about 18; (b) a z-average molecular weight to number-average molecular weight ratio, Mz / Mn, of from about 8 to about 40; (c) a z-average molecular weight to weight-average molecular weight ratio, Mz / Mw, of from about 2 to about 5; (d) a number-average molecular weight, Mn, of from about 5 kg / mol to about 25 kg / mol; (e) a weight-average molecular weight, Mw, of from about 60 kg / mol to about 180 kg / mol; and (f) a z-average molecular weight, Mz, of from about 180 kg / mol to about 350 kg / mol.

[0443] Embodiment VII. The ethylene polymer product of any one of embodiments I to VI, wherein the first weight-average molecular weight, Mw,1, and the second weight-average molecular weight, Mw,2, satisfy the inequality 2 < Mw,1 / Mw,2 < 20.

[0444] Embodiment VIII. The ethylene polymer product of any one of embodiments I to VII, wherein the bimodal polyethylene blend is an in-situ blend.

[0445] Embodiment IX. The ethylene polymer product of embodiment VIII, wherein the bimodal polyethylene blend is produced in a continuous solution-phase polymerization process, the continuous solution-phase polymerization process comprising: forming a first ethylene polymer in a first solution-phase polymerization reactor in the presence of a first single site catalyst system; and forming a second ethylene polymer in a second solutionphase polymerization reactor in the presence of a second single site catalyst system.

[0446] Embodiment X. The ethylene polymer product of embodiment IX, wherein the first single site catalyst system and the second single site catalyst system are independently chosen and each comprise an unbridged phosphinimine catalyst.

[0447] Embodiment XI. The ethylene polymer product of embodiment X, wherein the first single site catalyst system and the second single site catalyst system both comprise the same unbridged phosphinimine catalyst.Embodiment XII. The ethylene polymer product of any one of embodiments IX to XI, wherein the first solution-phase polymerization reactor and the second solution-phase polymerization reactor are configured in series with one another.

[0448] Embodiment XIII. The ethylene polymer product of any one of embodiments I to XII, wherein: the first ethylene polymer has a weight percent of from about 30 weight percent to about 70 weight percent, based on the total weight of the bimodal polyethylene blend; and the second ethylene polymer has a weight percent of from about 30 weight percent to about 70 weight percent, based on the total weight of the bimodal polyethylene blend.

[0449] Embodiment XIV. The ethylene polymer product of any one of embodiments I to XIII, wherein the first ethylene polymer has a weight percent of greater than 50 weight percent, based on the total weight of the bimodal polyethylene blend.

[0450] Embodiment XV. The ethylene polymer product of any one of embodiments I to XIII, wherein the second ethylene polymer has a weight percent of greater than 50 weight percent, based on the total weight of the bimodal polyethylene blend.

[0451] Embodiment XVI. The ethylene polymer product of any one of embodiments I to XV, wherein the first ethylene polymer, the second ethylene polymer and the third ethylene polymer are each an ethylene homopolymer.

[0452] Embodiment XVII. The ethylene polymer product of any one of embodiments I to XVI, wherein the third ethylene polymer has a heat of fusion of greater than 200 I / g, as determined by differential scanning calorimetry.

[0453] Embodiment XVIII. The ethylene polymer product of any one of embodiments I to XVII, wherein the third ethylene polymer has a melting point of greater than 110°C, as determined by differential scanning calorimetry.

[0454] Embodiment XIX. The ethylene polymer product of any one of embodiments I to XVIII, wherein the third ethylene polymer contains greater than about 60 weight percent, based on the total weight of the third ethylene polymer, of material having a molecular weight of greater than 1,000 g / mol and less than 10,000 g / mol.

[0455] Embodiment XX. The ethylene polymer product of any one of embodiments I to XVIII, wherein the third ethylene polymer contains greater than about 70 weight percent, based on the total weight of the third ethylene polymer, of material having a molecular weight of greater than 1,000 g / mol and less than 10,000 g / mol.Embodiment XXI. The ethylene polymer product of any one of embodiments I to XX, wherein the third ethylene polymer has a third polydispersity index, Mw,3 / Mn,3, satisfying the inequalities: 1< Mw,3 / Mn,3 < 1.5×Mw,1 / Mn,1 and 1< Mw,3 / Mn,3 < 1.5×Mw,2 / Mn,2.

[0456] Embodiment XXII. The ethylene polymer product of embodiment XXI, wherein the third ethylene polymer has a third poly dispersity index, Mw,3 / Mn,3, of from greater than 1 to less than about 3.

[0457] Embodiment XXIII. The ethylene polymer product of any one of embodiments I to XXII, wherein the ethylene polymer product has an overall density of greater than about 0.950 g / cm3and an overall melt index I2 of from about 0.5 g / 10 minute to about 15 g / 10 minute.

[0458] Embodiment XXIV. A film layer comprising the ethylene polymer product of any one of embodiments I to XXIII.

[0459] Embodiment XXV. A multilayer film structure comprising the film layer of embodiment XXIV.

[0460] Embodiment XXVI. A film layer comprising an ethylene polymer product, the ethylene polymer product comprising: A) a bimodal polyethylene blend, the bimodal polyethylene blend comprising: from about 30 weight percent to about 70 weight percent, based on the total weight of the bimodal polyethylene blend, of a first ethylene polymer having a first weight-average molecular weight, Mw,1, of from about 50 kg / mol to about 250 kg / mol, a first poly dispersity index, Mw,1 / Mn,1, of from about 1.7 to about 2.5, and a first density ρ1 of greater than about 0.94 g / cm3; and from about 70 weight percent to about 30 weight percent, based on the total weight of the bimodal polyethylene blend, of a second ethylene polymer having a second weight-average molecular weight, Mw,2, of from about 8 kg / mol to about 30 kg / mol, a second poly dispersity index, Mw,2 / Mn,2, of from about 1.7 to about 2.5, and a second density pi of greater than about 0.95 g / cm3; and B) from about 1×102parts per million to about 1×105parts per million of a third ethylene polymer, based on the total weight of the bimodal polyethylene blend; wherein the third ethylene polymer has a melting point of greater than 80°C, as determined by differential scanning calorimetry; and wherein the third ethylene polymer has a third weight-average molecular weight, Mw,3, satisfying the inequality Mw,3 < Mw,2.

[0461] Embodiment XXVII. The film layer of embodiment XXVI, wherein the third ethylene polymer has a heat of fusion of greater than 200 J / g and a melting point of greater than 110°C, as determined by differential scanning calorimetry.Embodiment XXVIII. The film layer of embodiment XXVI or XXVII, wherein the third ethylene polymer has a third poly dispersity index, Mw,3 / Mn,3, of from greater than 1 to less than about 3.

[0462] Embodiment XXIX. The film layer of any one of embodiments XXVI to XXVIII, wherein the third ethylene polymer contains greater than about 70 weight percent, based on the total weight of the third ethylene polymer, of material having a molecular weight of greater than 1,000 g / mol and less than 10,000 g / mol.

[0463] Embodiment XXX. The film layer of any one of embodiments XXVI to XXIX, wherein the bimodal polyethylene blend is further characterized by at least one of the following features: (a) a polydispersity index, Mw / Mn, of from about 4 to about 18; (b) a z-average molecular weight to number-average molecular weight ratio, Mz / Mn, of from about 8 to about 40; (c) a z-average molecular weight to weight-average molecular weight ratio, Mz / Mw, of from about 2 to about 5; (d) a number-average molecular weight, Mn, of from about 5 kg / mol to about 25 kg / mol; (e) a weight-average molecular weight, Mw, of from about 60 kg / mol to about 180 kg / mol; and (f) a z-average molecular weight, Mz, of from about 180 kg / mol to about 350 kg / mol.

[0464] Embodiment XXXI. The film layer of any one of embodiments XXVI to XXX, wherein the bimodal polyethylene blend is an in-situ blend.

[0465] Embodiment XXXII. The film layer of any one of embodiments XXVI to XXXI, wherein the first ethylene polymer, the second ethylene polymer and the third ethylene polymer are each an ethylene homopolymer.

[0466] Embodiment XXXIII. The film layer of any one of embodiments XXVI to XXXII, wherein the ethylene polymer product has an overall density of greater than about 0.950 g / cm3and an overall melt index I2of from about 0.5 g / 10 minute to about 15 g / 10 minute.

[0467] Embodiment XXXIV. The film layer of any one of embodiments XXVI to XXXIII, wherein the film layer is a blown film layer.

[0468] Embodiment XXXV. The film layer of embodiment XXXIV, wherein the film layer has a normalized water vapor transmission rate, nWVTR, of 0.10 g / 100 in2 / day or less at a film thickness of about 1.5 mil, wherein the normalized water vapor transmission rate is determined by multiplying the experimentally measured WVTR at 38°C and a relative humidity of 100% by the actual film thickness in mils and subsequently dividing the result by 1.5 mils.

[0469] Embodiment XXXVI. The film layer of embodiment XXXV, wherein the ethylene polymer product comprises: C) from about 1 x 102parts per million to about 3×103parts permillion of a nucleating agent, based on the total weight of the bimodal polyethylene blend; and D) from about 5×102parts per million to about 1 x 104parts per million of an inorganic anti-blocking additive, based on the total weight of the bimodal polyethylene blend.

[0470] Embodiment XXXVII. The film layer of embodiment XXXIV or XXXV, wherein the film layer has a normalized oxygen transmission rate, nOTR, of 30 cm3 / 100 in2 / day or less at a film thickness of about 1.5 mil, wherein the normalized oxygen transmission rate is determined by multiplying the experimentally measured OTR at 23 °C and at a relative humidity of 0% by the actual film thickness in mils and subsequently dividing the result by 1.5 mils.

[0471] Embodiment XXXVIII. The film layer of embodiment XXXVII, wherein the ethylene polymer product comprises: C) from about 1 x 102parts per million to about 3 x 103parts per million of a nucleating agent, based on the total weight of the bimodal polyethylene blend; and D) from about 5×102parts per million to about 1 x 104parts per million of an inorganic anti-blocking additive, based on the total weight of the bimodal polyethylene blend.

[0472] Embodiment XXXIX. The film layer of embodiment XXXVI or XXXVIII, wherein the nucleating agent comprises a calcium salt of 1,2-cyclohexanedicarboxylic acid.

[0473] Embodiment XL. The film layer of embodiment XXXVI, XXXVIII or XXXIX, wherein the inorganic anti-blocking additive comprises talc.

[0474] Embodiment XLI. A multilayer film structure comprising the film layer of any one of embodiment XXVI to XL.

[0475] Embodiment XLII. The multilayer film structure of embodiment XLI, wherein the film layer is a skin layer.

[0476] Embodiment XLIII. A multilayer film structure, comprising at least one skin layer comprising an ethylene polymer product, the ethylene polymer product comprising: A) a bimodal polyethylene blend, the bimodal polyethylene blend comprising: from about 30 weight percent to about 70 weight percent, based on the total weight of the bimodal polyethylene blend, of a first ethylene polymer having a first weight-average molecular weight, Mw,1, of from about 50 kg / mol to about 250 kg / mol, a first poly dispersity index, Mw,1 / Mn,1, of from about 1.7 to about 2.5, and a first density ρ1 of greater than about 0.94 g / cm3; and from about 70 weight percent to about 30 weight percent, based on the total weight of the bimodal polyethylene blend, of a second ethylene polymer having a second weight-average molecular weight, Mw,2, of from about 8 kg / mol to about 30 kg / mol, a second poly dispersity index, Mw,2 / Mn,2, of from about 1.7 to about 2.5, and a second densitypi of greater than about 0.95 g / cm3; B) from about 1×102parts per million to about 1×105parts per million of a third ethylene polymer, based on the total weight of the bimodal polyethylene blend; wherein the third ethylene polymer has a melting point of greater than 80°C, as determined by differential scanning calorimetry; and wherein the third ethylene polymer has a third weight-average molecular weight, Mw,3, satisfying the inequality Mw,3 < Mw,2; C) from about IxlO2parts per million to about 3xl03parts per million of a nucleating agent, based on the total weight of the bimodal polyethylene blend; and D) from about 5×102parts per million to about 1×104parts per million of an inorganic anti-blocking additive, based on the total weight of the bimodal polyethylene blend.

[0477] Embodiment XLIV The multilayer film structure of embodiment XLIII, wherein the nucleating agent comprises a calcium salt of 1,2-cyclohexanedicarboxylic acid.

[0478] Embodiment XLV. The multilayer film structure of embodiment XLIII or XLIV, wherein the inorganic anti-blocking additive comprises talc.

[0479] Embodiment XLVI. The multilayer film structure of any one of embodiments XLIII to XLV, wherein the third ethylene polymer has a heat of fusion of greater than 200 J / g and a melting point of greater than 110°C, as determined by differential scanning calorimetry.

[0480] Embodiment XLVII. The multilayer film structure of any one of embodiments XLIII to XLVI, wherein the third ethylene polymer has a third poly dispersity index, Mw,3 / Mn,3, of from greater than 1 to less than about 3.

[0481] Embodiment XLVIII. The multilayer film structure of any one of embodiments XLVIII to XLVII, wherein the third ethylene polymer contains greater than about 70 weight percent, based on the total weight of the third ethylene polymer, of material having a molecular weight of greater than 1,000 g / mol and less than 10,000 g / mol.

[0482] Embodiment XLIX. The multilayer film structure of any one of embodiments XLIII to XLVIII, wherein the bimodal polyethylene blend is further characterized by at least one of the following features: (a) a poly dispersity index, A- / LU, of from about 4 to about 18; (b) a z-average molecular weight to number-average molecular weight ratio, Mz / Mn, of from about 8 to about 40; (c) a z-average molecular weight to weight-average molecular weight ratio, Mz / Mw, of from about 2 to about 5; (d) a number-average molecular weight, Mn, of from about 5 kg / mol to about 25 kg / mol; (e) a weight-average molecular weight, Mw, of from about 60 kg / mol to about 180 kg / mol; and (f) a z-average molecular weight, Mz, of from about 180 kg / mol to about 350 kg / mol.

[0483] Embodiment L. The of any one of embodiments XLIII to XLIX, wherein the bimodal polyethylene blend is an in-situ blend.Embodiment LI. The multilayer film structure of any one of embodiments XLIII to LI, wherein the first ethylene polymer, the second ethylene polymer and the third ethylene polymer are each an ethylene homopolymer.

[0484] Embodiment LIL The multilayer film structure of any one of embodiments XLIII to LI, wherein the ethylene polymer product has an overall density of greater than about 0.950 g / cm3and an overall melt index I2of from about 0.5 g / 10 minute to about 15 g / 10 minute.

[0485] INDUSTRIAL APPLICABILITY

[0486] The present disclosure provides ethylene polymer products that, when converted into film, exhibit good barrier properties. The resulting films are suitable for applications such as food packaging.

Claims

CLAIMS1. An ethylene polymer product, comprising:A) a bimodal polyethylene blend, the bimodal polyethylene blend comprising:a first ethylene polymer having a first weight-average molecular weight, v,i, of from about 50 kg / mol to about 250 kg / mol, a first poly dispersity index, Afw,i / Mn,i, of from about 1.7 to about 2.5, and a first density ρ1 of greater than about 0.94 g / cm3; anda second ethylene polymer having a second weight-average molecular weight, V,2, of from about 8 kg / mol to about 30 kg / mol, a second poly dispersity index, v,2 / Mn,2, of from about 1.7 to about 2.5, and a second density pi of greater than about 0.95 g / cm3; andB) from about 1×102parts per million to about 1×105parts per million of a third ethylene polymer, based on the total weight of the bimodal polyethylene blend;wherein the third ethylene polymer has a melting point of greater than 80°C, as determined by differential scanning calorimetry; andwherein the third ethylene polymer has a third weight-average molecular weight, Mw,3, satisfying the inequality Mw,3 < Mw,2.

2. The ethylene polymer product of claim 1, wherein the ethylene polymer product further comprises C) from about 1 x 102parts per million to about 3 x 103parts per million of a nucleating agent, based on the total weight of the bimodal polyethylene blend.

3. The ethylene polymer product of claim 2, wherein the nucleating agent comprises a calcium salt of 1,2-cyclohexanedicarboxylic acid.

4. The ethylene polymer product of any one of claims 1-3, wherein the ethylene polymer product further comprises D) from about 5×102parts per million to about 104parts per million of an inorganic anti-blocking additive, based on the total weight of the bimodal polyethylene blend.

5. The ethylene polymer product of claim 4, wherein the inorganic anti -blocking additive comprises talc.

6. The ethylene polymer product of any one of claims 1-5, wherein the bimodal polyethylene blend is further characterized by at least one of the following features:(I) a poly dispersity index, Mw / Mn, of from about 4 to about 18;(II) a z-average molecular weight to number-average molecular weight ratio, Mz / Mn, of from about 8 to about 40;(III) a z-average molecular weight to weight-average molecular weight ratio, MJM, of from about 2 to about 5;(IV) a number-average molecular weight, Mn, of from about 5 kg / mol to about 25 kg / mol;(V) a weight-average molecular weight, Mw, of from about 60 kg / mol to about 180 kg / mol; and(VI) a z-average molecular weight, Mz, of from about 180 kg / mol to about 350 kg / mol.

7. The ethylene polymer product of any one of claims 1-6, wherein the first weightaverage molecular weight, Mw,1, and the second weight-average molecular weight, Mw,2, satisfy the inequality 2 < Mw,1 / Mw,2 < 20.

8. The ethylene polymer product of any one of claims 1-7, wherein the bimodal polyethylene blend is an in-situ blend.

9. The ethylene polymer product of claim 8, wherein the bimodal polyethylene blend is produced in a continuous solution-phase polymerization process, the continuous solutionphase polymerization process comprising:forming a first ethylene polymer in a first solution-phase polymerization reactor in the presence of a first single site catalyst system; andforming a second ethylene polymer in a second solution-phase polymerization reactor in the presence of a second single site catalyst system.

10. The ethylene polymer product of claim 9, wherein the first single site catalyst system and the second single site catalyst system are independently chosen and each comprise an unbridged phosphinimine catalyst.

11. The ethylene polymer product of claim 10, wherein the first single site catalyst system and the second single site catalyst system both comprise the same unbridged phosphinimine catalyst.

12. The ethylene polymer product of any one of claims 9-11, wherein the first solutionphase polymerization reactor and the second solution-phase polymerization reactor are configured in series with one another.

13. The ethylene polymer product of any one of claims 1-12, wherein:the first ethylene polymer has a weight percent of from about 30 weight percent to about 70 weight percent, based on the total weight of the bimodal polyethylene blend; and the second ethylene polymer has a weight percent of from about 30 weight percent to about 70 weight percent, based on the total weight of the bimodal polyethylene blend.

14. The ethylene polymer product of any one of claims 1-13, wherein the first ethylene polymer has a weight percent of greater than 50 weight percent, based on the total weight of the bimodal polyethylene blend.

15. The ethylene polymer product of any one of claims 1-13, wherein the second ethylene polymer has a weight percent of greater than 50 weight percent, based on the total weight of the bimodal polyethylene blend.

16. The ethylene polymer product of any one of claims 1-15, wherein the first ethylene polymer, the second ethylene polymer and the third ethylene polymer are each an ethylene homopolymer.

17. The ethylene polymer product of any one of claims 1-16, wherein the third ethylene polymer has a heat of fusion of greater than 200 J / g, as determined by differential scanning calorimetry.

18. The ethylene polymer product of any one of claims 1-17, wherein the third ethylene polymer has a melting point of greater than 110°C, as determined by differential scanning calorimetry.

19. The ethylene polymer product of any one of claims 1-18, wherein the third ethylene polymer contains greater than about 60 weight percent, based on the total weight of the third ethylene polymer, of material having a molecular weight of greater than 1,000 g / mol and less than 10,000 g / mol.

20. The ethylene polymer product of any one of claims 1-18, wherein the third ethylene polymer contains greater than about 70 weight percent, based on the total weight of the third ethylene polymer, of material having a molecular weight of greater than 1,000 g / mol and less than 10,000 g / mol.

21. The ethylene polymer product of any one of claims 1-20, wherein the third ethylene polymer has a third poly dispersity index, v,3 / Mn,3, satisfying the inequalities: 1 < AA.3 / M11.3 < 1.5xA / w,l / Mn,l and 1 < A / w,3 / Mn,3 < 1.5* v,2 / Mn,2.

22. The ethylene polymer product of any one of claims 1-20, wherein the third ethylene polymer has a third poly dispersity index, Mw,3 / Mn,3, of from greater than 1 to less than about 3.

23. The ethylene polymer product of any one of claims 1-22, wherein the ethylene polymer product has an overall density of greater than about 0.950 g / cm3and an overall melt index I2of from about 0.5 g / 10 minute to about 15 g / 10 minute.

24. A film layer comprising the ethylene polymer product of any one of claims 1-23.

25. A multilayer film structure comprising the film layer of claim 24.

26. A film layer comprising an ethylene polymer product, the ethylene polymer product comprising:A) a bimodal polyethylene blend, the bimodal polyethylene blend comprising:from about 30 weight percent to about 70 weight percent, based on the total weight of the bimodal polyethylene blend, of a first ethylene polymer having a first weight-average molecular weight, Mw,1, of from about 50 kg / mol to about 250 kg / mol, a first polydispersity index, Mw,1 / Mn,1, of from about 1.7 to about 2.5, and a first density ρ1 of greater than about 0.94 g / cm3; andfrom about 70 weight percent to about 30 weight percent, based on the total weight of the bimodal polyethylene blend, of a second ethylene polymer having a second weight-average molecular weight, Mw,2, of from about 8 kg / mol to about 30 kg / mol, a second poly dispersity index, Mw,2 / Mn,2, of from about 1.7 to about 2.5, and a second density pi of greater than about 0.95 g / cm3; andB) from about 1×102parts per million to about 1×105parts per million of a third ethylene polymer, based on the total weight of the bimodal polyethylene blend;wherein the third ethylene polymer has a melting point of greater than 80°C, as determined by differential scanning calorimetry; andwherein the third ethylene polymer has a third weight-average molecular weight, V,3, satisfying the inequality v,3 < Afw,2.

27. The film layer of claim 26, wherein the third ethylene polymer has a heat of fusion of greater than 200 J / g and a melting point of greater than 110°C, as determined by differential scanning calorimetry.

28. The film layer of claim 26 or 27, wherein the third ethylene polymer has a third poly dispersity index, Mw,3 / Mn,3, of from greater than 1 to less than about 3.

29. The film layer of any one of claims 26-28, wherein the third ethylene polymer contains greater than about 70 weight percent, based on the total weight of the third ethylene polymer, of material having a molecular weight of greater than 1,000 g / mol and less than 10,000 g / mol.

30. The film layer of any one of claims 26-29, wherein the bimodal polyethylene blend is further characterized by at least one of the following features:(I) a poly dispersity index, Mw / Mn, of from about 4 to about 18;(II) a z-average molecular weight to number-average molecular weight ratio, Mz / Mn, of from about 8 to about 40;(III) a z-average molecular weight to weight-average molecular weight ratio, MJM, of from about 2 to about 5;(IV) a number-average molecular weight, Mn, of from about 5 kg / mol to about 25 kg / mol;(V) a weight-average molecular weight, Mw, of from about 60 kg / mol to about 180 kg / mol; and(VI) a z-average molecular weight, Mz, of from about 180 kg / mol to about 350 kg / mol.

31. The film layer of any one of claims 26-30, wherein the bimodal polyethylene blend is an in-situ blend.

32. The film layer of any one of claims 26-31, wherein the first ethylene polymer, the second ethylene polymer and the third ethylene polymer are each an ethylene homopolymer.

33. The film layer of any one of claims 26-32, wherein the ethylene polymer product has an overall density of greater than about 0.950 g / cm3and an overall melt index I2of from about 0.5 g / 10 minute to about 15 g / 10 minute.

34. The film layer of any one of claims 26-33, wherein the film layer is a blown film layer.

35. The film layer of claim 34, wherein the film layer has a normalized water vapor transmission rate, nWVTR, of 0.10 g / 100 in2 / day or less at a film thickness of about 1.5 mil, wherein the normalized water vapor transmission rate is determined by multiplying the experimentally measured WVTR at 38°C and a relative humidity of 100% by the actual film thickness in mils and subsequently dividing the result by 1.5 mils.

36. The film layer of claim 35, wherein the ethylene polymer product comprises:C) from about 1 x 102parts per million to about 3×103parts per million of a nucleating agent, based on the total weight of the bimodal polyethylene blend; andD) from about 5×102parts per million to about 1 x 104parts per million of an inorganic anti-blocking additive, based on the total weight of the bimodal polyethylene blend.

37. The film layer of claim 34 or 35, wherein the film layer has a normalized oxygen transmission rate, nOTR, of 30 cm3 / 100 in2 / day or less at a film thickness of about 1.5 mil, wherein the normalized oxygen transmission rate is determined by multiplying the experimentally measured OTR at 23 °C and at a relative humidity of 0% by the actual film thickness in mils and subsequently dividing the result by 1.5 mils.

38. The film layer of claim 37, wherein the ethylene polymer product comprises:C) from about 1 x 102parts per million to about 3×103parts per million of a nucleating agent, based on the total weight of the bimodal polyethylene blend; andD) from about 5×102parts per million to about 1 x 104parts per million of an inorganic anti-blocking additive, based on the total weight of the bimodal polyethylene blend.

39. The film layer of claim 36 or 38, wherein the nucleating agent comprises a calcium salt of 1,2-cyclohexanedicarboxylic acid.

40. The film layer of claim 36, 38 or 39, wherein the inorganic anti-blocking additive comprises talc.

41. A multilayer film structure comprising the film layer of any one of claims 26-40.

42. The multilayer film structure of claim 41, wherein the film layer is a skin layer.

43. A multilayer film structure, comprising at least one skin layer comprising an ethylene polymer product, the ethylene polymer product comprising:A) a bimodal polyethylene blend, the bimodal polyethylene blend comprising:from about 30 weight percent to about 70 weight percent, based on the total weight of the bimodal polyethylene blend, of a first ethylene polymer having a first weight-average molecular weight, Mw,1, of from about 50 kg / mol to about 250 kg / mol, a first polydispersity index, Mw,1 / Mn,1, of from about 1.7 to about 2.5, and a first density ρ1 of greater than about 0.94 g / cm3; andfrom about 70 weight percent to about 30 weight percent, based on the total weight of the bimodal polyethylene blend, of a second ethylene polymer having a second weight-average molecular weight, Mw,2, of from about 8 kg / mol to about 30 kg / mol, a second poly dispersity index, Mw,2 / Mn,2, of from about 1.7 to about 2.5, and a second density pi of greater than about 0.95 g / cm3;B) from about 1×102parts per million to about 1×105parts per million of a third ethylene polymer, based on the total weight of the bimodal polyethylene blend;wherein the third ethylene polymer has a melting point of greater than 80°C, as determined by differential scanning calorimetry; andwherein the third ethylene polymer has a third weight-average molecular weight, V,3, satisfying the inequality Mp < A / w,2;C) from about 1 x 102parts per million to about 3 x 103parts per million of a nucleating agent, based on the total weight of the bimodal polyethylene blend; andD) from about 5×102parts per million to about 1 x 104parts per million of an inorganic anti-blocking additive, based on the total weight of the bimodal polyethylene blend.

44. The multilayer film structure of claim 43, wherein the nucleating agent comprises a calcium salt of 1,2-cyclohexanedicarboxylic acid.

45. The multilayer film structure of claim 43 or 44, wherein the inorganic anti -blocking additive comprises talc.

46. The multilayer film structure of any one of claims 43-45, wherein the third ethylene polymer has a heat of fusion of greater than 200 J / g and a melting point of greater than 110°C, as determined by differential scanning calorimetry.

47. The multilayer film structure of any one of claims 43-46, wherein the third ethylene polymer has a third poly dispersity index, Mw,3 / Mn,3, of from greater than 1 to less than about 3.

48. The multilayer film structure of any one of claims 43-47, wherein the third ethylene polymer contains greater than about 70 weight percent, based on the total weight of the third ethylene polymer, of material having a molecular weight of greater than 1,000 g / mol and less than 10,000 g / mol.

49. The multilayer film structure of any one of claims 43-48, wherein the bimodal polyethylene blend is further characterized by at least one of the following features:(I) a polydispersity index, Mw / Mn, of from about 4 to about 18;(II) a z-average molecular weight to number-average molecular weight ratio, Mz / Mn, of from about 8 to about 40;(III) a z-average molecular weight to weight-average molecular weight ratio, MJM, of from about 2 to about 5;(IV) a number-average molecular weight, Mn, of from about 5 kg / mol to about 25 kg / mol;(V) a weight-average molecular weight, Mw, of from about 60 kg / mol to about 180 kg / mol; and(VI) a z-average molecular weight, Mz, of from about 180 kg / mol to about 350 kg / mol.

50. The of any one of claims 43-49, wherein the bimodal polyethylene blend is an in-situ blend.

51. The multilayer film structure of any one of claims 43-50, wherein the first ethylene polymer, the second ethylene polymer and the third ethylene polymer are each an ethylene homopolymer.

52. The multilayer film structure of any one of claims 43-51, wherein the ethylene polymer product has an overall density of greater than about 0.950 g / cm3and an overall melt index I2 of from about 0.5 g / 10 minute to about 15 g / 10 minute.

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